Pesticidally active azole-amide compounds

ABSTRACT

Compounds of formula (I) wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides.

The present invention relates to pesticidally active, in particularinsecticidally active azole-amide compounds, to processes for theirpreparation, to compositions comprising those compounds, and to theiruse for controlling animal pests, including arthropods and in particularinsects or representatives of the order Acarina.

WO2017192385 describes certain heteroaryl-1,2,4-triazole andheteroaryl-tetrazole compounds for use for controlling ectoparasites inanimals (such as a mammal and a non-mammal animal). There have now beenfound novel pesticidally active-azole azine compounds.

The present invention accordingly relates, in a first aspect, to acompound of the formula I

wherein:

A₁ is N or CH;

R₁ is hydrogen, C₁-C₆alkyl, C₁-C₆cyanoalkyl, aminocarbonylC₁-C₆alkyl,hydroxycarbonylC₁-C₆alkyl, C₁-C₆nitroalkyl, trimethylsilaneC₁-C₆alkyl,C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₂-C₆haloalkynyl; C₃-C₄cycloalkylC₁-C₂alkyl- wherein the C₃-C₄cycloalkylis optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH₂—; orbenzyl optionally substituted with halo or C₁-C₆haloalkyl;R₂ is phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein thephenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionallysubstituted with one to three substituents, provided the substituent(s)are not on either carbon adjacent to the carbon C═O is attached, andeach substituent is independently selected from: C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃thiohaloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, NO₂, SF₅, CN, CONH₂, COOH and C(S)NH₂;R₃ is C₁-C₃alkyl or C₁-C₃haloalkyl;R₄ is C₁-C₆haloalkyl; C₂-C₆haloalkenyl, C₂-C₆haloalkynyl,C₃-C₄halocycloalkyl, C₃-C₆cycloalkylC₁-C₄haloalkyl;R₅ is H, C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl, C₁-C₃alkoxy,C₁-C₃alkoxycarbonyl, or di(C₁-C₃alkoxy)methine; or a stereoisomer,enantiomer, tautomer and N-oxide of the compound of formula I, oragrochemically acceptable salt thereof.

Compounds of formula I which have at least one basic centre can form,for example, acid addition salts, for example with strong inorganicacids such as mineral acids, for example perchloric acid, sulfuric acid,nitric acid, nitrous acid, a phosphorus acid or a hydrohalic acid, withstrong organic carboxylic acids, such as C₁-C₄alkanecarboxylic acidswhich are unsubstituted or substituted, for example by halogen, forexample acetic acid, such as saturated or unsaturated dicarboxylicacids, for example oxalic acid, malonic acid, succinic acid, maleicacid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids,for example ascorbic acid, lactic acid, malic acid, tartaric acid orcitric acid, or such as benzoic acid, or with organic sulfonic acids,such as C₁-C₄alkane- or arylsulfonic acids which are unsubstituted orsubstituted, for example by halogen, for example methane- orp-toluenesulfonic acid. Compounds of formula I which have at least oneacidic group can form, for example, salts with bases, for examplemineral salts such as alkali metal or alkaline earth metal salts, forexample sodium, potassium or magnesium salts, or salts with ammonia oran organic amine, such as morpholine, piperidine, pyrrolidine, a mono-,di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- ordimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, forexample mono-, di- or triethanolamine.

In each case, the compounds of formula I according to the invention arein free form, in oxidized form as a N-oxide or in salt form, e.g. anagronomically usable salt form.

N-oxides are oxidized forms of tertiary amines or oxidized forms ofnitrogen containing heteroaromatic compounds. They are described forinstance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra,CRC Press, Boca Raton 1991.

The compounds of formula I according to the invention also includehydrates which may be formed during the salt formation.

The term “C₁-C_(n)alkyl” as used herein refers to a saturatedstraight-chain or branched hydrocarbon radical attached via any of thecarbon atoms having 1 to n carbon atoms, for example, any one of theradicals methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or1-ethyl-2-methylpropyl.

The term “C₁-C_(n)haloalkyl” as used herein refers to a straight-chainor branched saturated alkyl radical attached via any of the carbon atomshaving 1 to n carbon atoms (as mentioned above), where some or all ofthe hydrogen atoms in these radicals may be replaced by fluorine,chlorine, bromine and/or iodine, i.e., for example, any one ofchloromethyl, dichloromethyl, trichloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl,2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl,2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl,2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl,2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl,3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl,1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl,1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutylor nonafluorobutyl. According a term “C₁-C₂fluoroalkyl” would refer to aC₁-C₂alkyl radical which carries 1, 2, 3, 4, or 5 fluorine atoms, forexample, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,1,1,2,2-tetrafluoroethyl or pentafluoroethyl.

The term “C₁-C_(n)alkoxy” as used herein refers to a straight-chain orbranched saturated alkyl radical having 1 to n carbon atoms (asmentioned above) which is attached via an oxygen atom, i.e., forexample, any one of the radicals methoxy, ethoxy, n-propoxy,1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or1,1-dimethylethoxy. The term “haloC₁-C_(n)alkoxy” as used herein refersto a C₁-C_(n)alkoxy radical where one or more hydrogen atoms on thealkyl radical is replaced by the same or different halo atom(s)—examplesinclude tnfluoromethoxy, 2-fiuoroetlioxy, 3-fluoropropoxy,3,3,3-trifluoropropoxy, 4-chlorobutoxy.

The term “C₁-C_(n)cyanoalkyl” as used herein refers to a straight chainor branched saturated C₁-C_(n)alkyl radical having 1 to n carbon atoms(as mentioned above), where one of the hydrogen atoms in these radicalsis be replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl,2-cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl,1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.

The term “C₃-C_(n)cycloalkyl” as used herein refers to 3-n memberedcycloalkyl groups such as cyclopropane, cyclobutane, cyclopentane andcyclohexane.

The term “C₃-C₄cycloalkyl-C₁-C₂alkyl-” as used herein refers to 3 or 4membered cycloalkyl group with either a methylene or ethylene group,which methylene or ethylene group is connected to the rest of themolecule. In the instance, the C₃-C₄cycloalkyl-C₁-C₂alkyl- group issubstituted, the substituent(s) is on the cycloalkyl group.

The term “aminocarbonylC₁-C_(n)alkyl” as used herein refers to an alkylradical where one of the hydrogen atoms in the radical is replaced byCONH2 group.

The term “hydroxycarbonylC₁-C_(n)alkyl” as used herein refers to analkyl radical where one of the hydrogen atoms in the radical is replacedby COOH group.

The term “C₁-C_(n)nitroalkyl” as used herein refers to an alkyl radicalwhere one of the hydrogen atoms in the radical is replaced by NO2 group.

The term “C₁-C_(n)haloalkylthio” as used herein refers to aC₁-C₃haloalkyl moiety linked through a sulfur atom.

The term “trimethylsilaneC₁-C_(n)alkyl” as used herein refers to analkyl radical where one of the hydrogen atoms in the radical is replacedby a —Si(CH₃)₃ group.

The term “C₂-C_(n)alkenyl” as used herein refers to a straight orbranched alkenyl chain having from two to n carbon atoms and one or twodouble bonds, for example, ethenyl, prop-I-enyl, but-2-enyl.

The term “C₂-C_(n)haloalkenyl” as used herein refers to aC₂-C_(n)alkenyl moiety substituted with one or more halo atoms which maybe the same or different.

The term “C₂-C_(n)alkynyl” as used herein refers to a straight orbranched alkynyl chain having from two to n carbon atoms and one triplebond, for example, ethynyl, prop-2-ynyl, but-3-ynyl,

The term “C₂-C_(n)haloalkynyl” as used herein refers to aC₂-C_(n)alkynyl moiety substituted with one or more halo atoms which maybe the same or different.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl

The pyridine, pyrimidine, pyrazine and pyridazine groups (unsubstitutedor substituted) for R₂ and R₄ are each connected via a carbon atom onthe respective ring to the rest of the compound.

As used herein, the term “controlling” refers to reducing the number ofpests, eliminating pests and/or preventing further pest damage such thatdamage to a plant or to a plant derived product is reduced.

The staggered line as used herein, for example, in K₁ and J₁, representthe point of connection/attachment to the rest of the compound.

As used herein, the term “pest” refers to insects, and molluscs that arefound in agriculture, horticulture, forestry, the storage of products ofvegetable origin (such as fruit, grain and timber); and those pestsassociated with the damage of man-made structures. The term pestencompasses all stages in the life cycle of the pest.

As used herein, the term “effective amount” refers to the amount of thecompound, or a salt thereof, which, upon single or multiple applicationsprovides the desired effect.

An effective amount is readily determined by the skilled person in theart, by the use of known techniques and by observing results obtainedunder analogous circumstances. In determining the effective amount anumber of factors are considered including, but not limited to: the typeof plant or derived product to be applied; the pest to be controlled &its lifecycle; the particular compound applied; the type of application;and other relevant circumstances.

As one of ordinary skill in the art will appreciate, compounds offormula I contain a stereogenic centre which is indicated with anasterisk in the structure below:

where R₁, R₂, R₃, R₄, and A₁ are as defined in the first aspect.

The present invention contemplates both racemates and individualenantiomers. Compounds having preferred stereochemistry are set outbelow.

Particularly preferred compounds of the present invention are compoundsof formula I′a:

where R₁, R₂, R₃, R₄, and A₁ are as defined in the first aspect, andstereoisomers, enantiomers, tautomers and N-oxides of the compounds offormula (I′a), and agrochemically acceptable salts thereof.

The term “optionally substituted” as used herein means that the groupreferenced is either unsubstituted or is substituted by a designatedsubstituent, for example, “C₃-C₄cycloalkyl is optionally substitutedwith 1 or 2 halo atoms” means C₃-C₄cycloalkyl, C₃-C₄cycloalkylsubstituted with 1 halo atom and C₃-C₄cycloalkyl substituted with 2 haloatoms.

Embodiments according to the invention are provided as set out below.

In an embodiment of each aspect of the invention, A₁ is

-   -   A. A₁ is N; or    -   B. A₁ is CH.

In an embodiment of each aspect of the invention, R₁ is

-   -   A. hydrogen; C₁-C₆alkyl optionally substituted with one        substituent selected from: CN, CONH₂, COOH, NO₂, and —Si(CH₃)₃;        C₁-C₆haloalkyl; C₂-C₆alkenyl; C₂-C₆alkynyl; C₂-C₆haloalkynyl;        C₃-C₄cycloalkyl-C₁-C₂alkyl- wherein the C₃-C₄cycloalkyl- is        optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH₂—;        or benzyl optionally substituted with halo or C₁-C₃haloalkyl; or    -   B. hydrogen; C₁-C₆haloalkyl; C₁-C₆alkyl optionally substituted        with CN or Si(CH₃)₃; C₃-C₆alkynyl; C₃-C₄cycloalkyl-C₁-C₂alkyl        wherein the C₃-C₄cycloalkyl is optionally substituted with 1 or        2 halo atoms; oxetan-3-yl-CH₂—; or benzyl optionally substituted        with halo; or    -   C. hydrogen, C₁-C₆alkyl, C₃-C₄cycloalkylC₁-C₂alkyl- wherein the        C₃-C₄cycloalkyl is optionally substituted with 1 or 2 halo        atoms, or oxetan-3-yl-CH₂—; or    -   D. hydrogen, C₁-C₆alkyl, or C₃-C₄cycloalkylC₁-C₂alkyl-; or    -   E. hydrogen; C₁-C₆haloalkyl; C₁-C₆alkyl optionally substituted        with CN or Si(CH₃)₃; C₃-C₆alkynyl; or C₃-C₄cycloalkyl-C₁-C₂alkyl        wherein the C₃-C₄cycloalkyl is optionally substituted with 1 or        2 halo atoms; or    -   F. hydrogen; C₁-C₆haloalkyl; C₁-C₆alkyl; C₃-C₆alkynyl; or        C₃-C₄cycloalkyl-C₁-C₂alkyl wherein the C₃-C₄cycloalkyl is        optionally substituted with 1 or 2 halo atoms; or    -   G. cyclopropyl-CH₂—, n-propyl, CH≡CCH₂—, CF₃CH₂CH₂—, FCH₂CH₂—,        FCH₂CH₂CH₂—, 2,2-difluorocyclopropyl-CH₂—,        2,2-dichlorocyclopropyl-CH₂—, hydrogen, CH₃, (CH₃)₃SiCH₂—,        CH₃CH₂—, or CNCH₂—; or    -   H. cyclopropyl-CH₂—, n-propyl, CH≡CCH₂—, CF₃CH₂CH₂—, FCH₂CH₂—,        FCH₂CH₂CH₂—, 2,2-difluorocyclopropyl-CH₂- or        2,2-dichlorocyclopropyl-CH₂—; or    -   I. cyclopropyl-CH₂—, n-propyl, CH≡CCH₂—, CF₃CH₂CH₂—, FCH₂CH₂—,        FCH₂CH₂CH₂—, 2,2-difluorocyclopropyl-CH₂—, hydrogen, CH₃,        (CH₃)₃SiCH₂—, or CH₃CH₂—; or    -   J. cyclopropyl-CH₂—, n-propyl, CH≡CCH₂—, CF₃CH₂CH₂—, FCH₂CH₂—,        FCH₂CH₂CH₂—, or 2,2-difluorocyclopropyl-CH₂—; or    -   K. cyclopropyl-CH₂—, n-propyl, CH≡CCH₂—, CF₃CH₂CH₂—, FCH₂CH₂—,        or FCH₂CH₂CH₂—; or    -   L. cyclopropyl-CH₂—, CH≡CCH₂—, hydrogen or CH₃; or    -   M. CH≡CCH₂— or cyclopropyl-CH₂—; or    -   N. cyclopropyl-CH₂—; or    -   O. cyclopropyl-CH₂—, hydrogen or CH₃; or    -   P. hydrogen.

In an embodiment of each aspect of the invention, R₂ is

-   -   A. phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein        the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is        optionally substituted with one to three substituents, provided        the substituent(s) are not on either carbon adjacent to the        carbon bonded to the —C(O)— group, each independently selected        from: C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃thiohaloalkyl,        C₁-C₃alkoxy, C₁-C₃haloalkoxy, halo, NO₂, SF₅, CN, CONH₂, COOH        and C(S)NH₂; or    -   B. phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein        the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is        optionally substituted with one to two substituents, provided        the substituent(s) are not on either carbon adjacent to the        carbon C═O is attached too, and each substituent is        independently selected from: C₁-C₃alkyl, C₁-C₃haloalkyl,        C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen or CN; or    -   C. phenyl, 3-pyridine or 4-pyridine substituted with one or two        substituents independently selected from: C₁-C₃haloalkyl,        C₁-C₃haloalkoxy, halo, CN, or C(S)NH₂, provided the        substituent(s) are not on either carbon adjacent to the carbon        bonded to the —C(O)— group; or    -   D. phenyl, 3-pyridine or 4-pyridine substituted with one or two        substituents independently selected from: C₁-C₃haloalkyl,        C₁-C₃haloalkoxy, halo, or CN, provided the substituent(s) are        not on either carbon adjacent to the carbon bonded to the —C(O)—        group; or    -   E. phenyl, or 3-pyridine substituted with one or two        substituents independently selected from: C₁-C₃haloalkyl,        C₁-C₃haloalkoxy, halo, or CN, provided the substituent(s) are        not on either carbon adjacent to the carbon bonded to the —C(O)—        group; or    -   F. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl,        3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl,        3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl,        5-trifluoromethylpyridin-3-yl, 3-bromo-5-trifluoromethylphenyl,        3-cyano-5-trifluoromethylphenyl or        2,6-bis(trifluoromethyl)pyridin-4-yl; or    -   G. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl,        3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl,        3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl,        5-trifluoromethylpyridi-3-yl, 3-bromo-5-trifluoromethylphenyi or        3-cyano-5-trifluoromethyl-phenyl; or    -   H. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl,        3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl,        3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl, or        5-trifluoromethylpyridin-3-yl; or    -   I. is 3,5-bis(trifluoromethyl)phenyl,        3-chloro-5-trifluoromethylphenyl, 3-cyanophenyL        3-chloro-5-trifluoromethoxyphenyl, 5-trifluoromethylpyridin-3-yl        or 3-cyano-5-trifluoromethyl phenyl; or    -   J. 3,5-bis(trifluoromethyl)phenyl,        3-chloro-5-trifluoromethylphenyl,        3-chloro-5-trifluoromethoxyphenyl or        5-trifluoromethpyridin-3-yl; or    -   K. 3,5-bis(trifluoromethyl)phenyl; or    -   L. one of K₁ to K₂₁ or

-   -   M. one of K₁, K₂, K₃, K₅, K₆, K₇, K₁₁, K₁₃ or K₁₅; or    -   N. K₁, K₂, K₅, K₆, K₇, K₁₁, K₁₃ or K₁₅; or    -   O. one of K₁, K₃, K₅, K₆, K₁₁, K₁₃ or K₁₅; or    -   P. one of K₁, K₅, K₆, K₁₁, K₁₃ or K₁₅; or    -   Q. one of K₁, K₃, or K₁₁; or    -   R. one of K₁, or K₁₁; or    -   S. one of K₁, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or        K₂₁; or    -   T. one of K₁, K₅, K₆, K₁₁, K₁₃, K₁₅, K₁₉, or K₂₀; or    -   U. one of K₁, K₆, K₁₁, K₁₅, K₁₉, or K₂₀; or    -   V. one of K₁, K₁₅, or K₂₀; or    -   W. K₁.

In an embodiment of each aspect of the invention, R₃ is

-   -   A. C₁-C₃alkyl or C₁-C₃haloalkyl; or    -   B. C₁-C₃alkyl; or    -   C. methyl.

In an embodiment of each aspect of the invention, R₄ is

-   -   A. C₁-C₆haloalkyl; C₂-C₆haloalkenyl, or C₂-C₆haloalkynyl, or        C₃-C₄halocycloalkyl; or    -   B. C₁-C₄haloalkyl; C₂-C₄haloalkenyl, or C₂-C₄haloalkynyl; or    -   C. C₁-C₄fluoroalkyl; C₂-C₄fluoroalkenyl, or C₂-C₄fluoroalkynyl;        or    -   D. trifluromethoxy, difluromethoxy, 2,2,2-trflurorethoxy,        2,2-diflurorethoxy, or 3,3,3-trifluororop-1-enoxy; or    -   E. trifluromethoxy or difluromethoxy; or    -   F. trifluromethoxy.

In an embodiment, the ring group containing the R₄ substituent isselected from J₁ to J₁₀

Preferably, the ring group is selected from J₁ to J₄; more preferably J₁or J₂.

In an embodiment of each aspect of the invention, R₅ is

-   -   A. hydrogen, halogen, CN, C₁-C₃alkyl, C₁-C₃haloalkyl,        C₃-C₄cycloalkyl, C₁-C₃alkoxy, or C₁-C₃haloalkoxy; or    -   B. hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl,        C₃-C₄cycloalkyl, C₁-C₃alkoxy, or C₁-C₃haloalkoxy; or    -   C. hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃haloalkoxy,        C₁-C₃alkoxy, or C₃-C₄cycloalkyl; or    -   D. hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl; or    -   E. hydrogen, halogen, C₁-C₃haloalkyl, or C₁-C₃alkoxy; or    -   F. hydrogen, C₁-C₃haloalkyl, or C₁-C₃alkoxy; or    -   G. C₁-C₃haloalkyl, or C₁-C₃alkoxy; or    -   H. hydrogen, methyl, CH₂CF₃, or cyclopropyl; or    -   I. methyl, CH₂CF₃, or cyclopropyl; or    -   J. hydrogen, methyl or (CH₂CH₂O)₂CH—; or    -   K. methyl or (CH₂CH₂O)₂CH—; or    -   L. hydrogen or methyl; or    -   M. hydrogen; or    -   N. methyl.

The present invention, accordingly, makes available a compound offormula I having the substituents R₁, R₂, R₃, R₄, R₅, and A₁ as definedabove in all combinations/each permutation. Accordingly, made available,for example, is a compound of formula I with A₁ being of the firstaspect (i.e. A₁ is N or CH); R₁ being embodiment D (i.e. hydrogen,C₁-C₆alkyl, or C₃-C₄cycloalkylC₁-C₂alkyl-); R₂ being an embodiment H(i.e. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl,3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl,3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl, or5-trifluoromethylpyridin-3-yl); R₃ being embodiment C (i.e. methyl); andR₄ being embodiment B (i.e. C₁-C₄haloalkyl; C₂-C₄haloalkenyl, orC₂-C₄haloalkynyl); and R5 being embodiment L (i.e hydrogen or methyl).

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, C₁-C₆alkyl, C₃-C₄cycloalkylC₁-C₂alkyl; asR₂ one of K₁, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or K₂₁: asR₃ methyl; as R₅ hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl;and as A₁ is N or CH; and as R₄ C₁-C₄haloalkyl; C₂-C₄haloalkenyl, orC₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, methyl, cyclopropylCH₂; as R₂ one of K₁,K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or K₂₁; as R₃ methyl; asR₅ hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl; and as A₁ is Nor CH; and as R₄ C₁-C₄haloalkyl; C₂-C₄haloalkenyl, or C₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, methyl, or cyclopropylCH₂; as R₂ one ofK₁, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or K₂₁; as R₃methyl; as R₅ hydrogen, methyl, CH₂CF₃, or cyclopropyl; and as A₁ is Nor CH; and as R₄ C₁-C₄haloalkyl; C₂-C₄haloalkenyl, or C₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, methyl, or cyclopropylCH₂; as R₂ one ofK₁, K₅, K₆, K₁₁, K₁₃, K₁₅, K₁₉, or K₂₀; as R₃ methyl; as R₅ hydrogen,methyl, CH₂CF₃, or cyclopropyl; and as A₁ is N or CH; and as R₄C₁-C₄haloalkyl; C₂-C₄haloalkenyl, or C₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, methyl, or cyclopropylCH₂; as R₂ one ofK₁, K₆, K₁₁, K₁₅, K₁₉, or K₂₀; as R₃ methyl; as R₅ hydrogen, methyl,CH₂CF₃, or cyclopropyl; and as A₁ is N or CH; and as R₄ C₁-C₄haloalkyl;C₂-C₄haloalkenyl, or C₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, methyl, or cyclopropylCH₂; as R₂ one ofK₁, K₁₅, or K₂₀; as R₃ methyl; as R₅ hydrogen, methyl, CH₂CF₃, orcyclopropyl; and as A₁ is N or CH; and as R₄ C₁-C₄haloalkyl;C₂-C₄haloalkenyl, or C₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, methyl, or cyclopropylCH₂; as R₂ one ofK₁, K₆, K₁₁, K₁₅, K₁₉, or K₂₀; as R₃ methyl; as R₅ hydrogen, methyl,CH₂CF₃, or cyclopropyl; and as A₁ is N or CH; and as R₄ trifluromethoxy,difluromethoxy, 2,2,2-trflurorethoxy, 2,2-diflurorethoxy, or3,3,3-trifluororop-1-enoxy.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, methyl, or cyclopropylCH₂; as R₂ one ofK₁, K₁₅, or K₂₀; as R₃ methyl; as R₅ hydrogen, methyl, CH₂CF₃, orcyclopropyl; and as A₁ is N or CH; and as R₄ trifluromethoxy,difluromethoxy, 2,2,2-trflurorethoxy, 2,2-diflurorethoxy, or3,3,3-trifluororop-1-enoxy.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, C₁-C₆alkyl, C₃-C₄cycloalkylC₁-C₂alkyl; asR₂ one of K₁, K₂, K₅, K₆, K₇, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, orK₂₁: as R₃ methyl; as R₅ hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl,C₃-C₄cycloalkyl; and as A₁ is N or CH; and as R₄ C₁-C₄haloalkyl,C₂-C₄haloalkenyl, or C₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, C₁-C₆alkyl, C₃-C₄cycloalkylC₁-C₂alkyl; asR₂ one of K₁, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or K₂₁: asR₃ methyl; as R₅ hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl;and as A₁ is N or CH; and as R₄ C₁-C₄haloalkyl, C₂-C₄haloalkenyl, orC₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, C₁-C₆alkyl, C₃-C₄cycloalkylC₁-C₂alkyl; asR₂ one of K₁, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or K₂₁: asR₃ methyl; as R₅ hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl;and as A₁ is N or CH; and as R₄ C₂-C₄haloalkenyl, or C₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ C₁-C₆alkyl, C₃-C₄cycloalkylC₁-C₂alkyl; as R₂ one ofK₁, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or K₂₁: as R₃methyl; as R₅ hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl; andas A₁ is N or CH; and as R₄ C₁-C₄haloalkyl; C₂-C₄haloalkenyl, orC₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ methyl, or cyclopropylCH₂; as R₂ one of K₁, K₅, K₆,K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or K₂₁; as R₃ methyl; as R₅hydrogen, methyl, CH₂CF₃, or cyclopropyl; and as A₁ is N or CH; and asR₄ trifluromethoxy, difluromethoxy, 2,2,2-trflurorethoxy,2,2-diflurorethoxy, or 3,3,3-trifluororop-1-enoxy.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, C₁-C₆alkyl, C₃-C₄cycloalkylC₁-C₂alkyl; asR₂ one of K₁, K₃, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₃, K₁₉, K₂₀, orK₂₁: as R₃ methyl; as R₅ C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl;and as A₁ is N or CH; and as R₄ C₁-C₄haloalkyl; C₂-C₄haloalkenyl, orC₂-C₄haloalkynyl.

In an embodiment of each aspect of the invention, the compound offormula I has as R₁ hydrogen, methyl, or cyclopropylCH₂; as R₂ one ofK₁, K₃, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₃, K₁₈, K₁₉, K₂₀, or K₂₁; as R₃methyl; as R₅ methyl, CH₂CF₃, or cyclopropyl; and as A₁ is N or CH; andas R₄ trifluromethoxy, difluromethoxy, 2,2,2-trflurorethoxy,2,2-diflurorethoxy, or 3,3,3-trifluororop-1-enoxy.

In a second aspect, the present invention makes available a compositioncomprising a compound of formula I as defined in the first aspect, oneor more auxiliaries and diluent, and optionally one more other activeingredient.

In a third aspect, the present invention makes available a method ofcombating and controlling insects, acarines, nematodes or molluscs whichcomprises applying to a pest, to a locus of a pest, or to a plantsusceptible to attack by a pest an insecticidally, acaricidally,nematicidally or molluscicidally effective amount of a compound asdefined in the first aspect or a composition as defined in the secondaspect.

In a fourth aspect, the present invention makes available a method forthe protection of plant propagation material from the attack by insects,acarines, nematodes or molluscs, which comprises treating thepropagation material or the site, where the propagation material isplanted, with an effective amount of a compound of formula I as definedin the first aspect or a composition as defined in the second aspect.

In a fifth aspect, the present invention makes available a plantpropagation material, such as a seed, comprising, or treated with oradhered thereto, a compound of formula I as defined in the first aspector a composition as defined in the second aspect.

In an embodiment of each aspect of the invention, compounds of formula Ihaving R₂ as 3,5-dichlorophenyl; R₃ as methyl; R₁ as hydrogen; R₄ asselected from 5-(difluoromethoxy)pyrimidin-2-yl,5-(trifluoromethoxy)pyrimidin-2-yl, 5-(difluoromethoxy)pyridin-2-yl,5-(trifluoromethoxy)pyridin-2-yl, 5-(trifluoromethoxy)pyridin-2-yl,5-(2,2,2-trifluoroethoxy)pyrdin-2-yl, 5-(pentafluoroethoxy)pyrdin-2-yl,and 5-(4,4,4-trifluorobutoxy)pyrdin-2-yl; and R₅ as hydrogen areexcluded from the present invention.

The present invention in a further aspect provides a method ofcontrolling parasites in or on an animal in need thereof comprisingadministering an effective amount of a compound of the first aspect. Thepresent invention further provides a method of controlling ectoparasiteson an animal in need thereof comprising administering an effectiveamount of a compound of formula I as defined om the first aspect. Thepresent invention further provides a method for preventing and/ortreating diseases transmitted by ectoparasites comprising administeringan effective amount of a compound of formula I as defined in the firstaspect, to an animal in need thereof.

Compounds of formula I can be prepared by those skilled in the artfollowing known methods. More specifically compounds of formulae I, andI′a, and intermediates therefor can be prepared as described below inthe schemes and examples. Certain stereogenic centers have been leftunspecified for the clarity and are not intended to limit the teachingof the schemes in any way.

The process according to the invention for preparing compounds offormula I is carried out by methods known to those skilled in the art.Compounds of formula I

can be prepared by reaction of an amine of formula II

Wherein R₁, R₃, R₄, R₅, and A₁ are as described in formula I, with acarboxylic acid derivative of formula III

wherein R₂ is described as above under formula I. The chemistry isdescribed in more detail in Scheme 1.

In Scheme 1, compounds of formula III wherein R₂ is described in formulaI, are activated to compounds of formula IIIa by methods known to thoseskilled in the art and described for example in Tetrahedron, 61 (46),10827-10852, 2005. For example, compounds where X₀ is halogen are formedby treatment of compounds of formula III with for example, oxalylchloride or thionyl chloride in the presence of catalytic quantities ofDMF in inert solvents such as methylene dichloride or THE attemperatures between 20° C. to 100° C., preferably 25° C. Treatment ofIIIa with compounds of formula II wherein R₁, R₃, R₄, R₅ and A₁ aredefined as above, optionally in the presence of a base, e.g.triethylamine or pyridine leads to compounds of formula I.Alternatively, compounds of formula I can be prepared by treatment ofcompounds of formula III with dicyclohexyl carbodiimide (DCC),1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium3-oxide hexafluorophosphate (HATU) to give the activated species IIIa,wherein X₀ is X₀₁, X₀₂ and X₀₃ respectively, in an inert solvent, e.g.pyridine, DMF, acetonitrile, CH₂Cl₂ or THE optionally in the presence ofa base, e.g. triethylamine, at temperatures between 30-180° C. Finally,an acid of the formula III can also be activated by reaction with acoupling reagent such as propanephosphonic acid anhydride (T3P®) toprovide compounds of formula IIIa wherein X₀ is X₀₄ as described forexample in Synthesis 2013, 45, 1569. Further reaction with an amine ofthe formula II provides compounds of formula I.

Compounds of formula IIa, wherein R₁, R₃, R₄, R₅ and A₁ are defined asabove, can be prepared by those skilled in the art. A typical example ofsuch a synthesis is shown in scheme 2.

For example, compounds of formula II may be prepared by reaction betweencompounds of formula VI, wherein R₃, R₄, R₅ and A₁ are as defined informula I, and compounds of formula VIII, wherein R₁ is defined informula I, in suitable solvents that may include, for example,acetonitrile or dioxane, in the presence of a suitable base, such assodium, potassium or cesium carbonate (or sodium or potassium hydrogencarbonate), usually upon heating at temperatures between roomtemperature and 200° C., preferably between 40° C. to the boiling pointof the reaction mixture, optionally under microwave heating conditions.

Compounds of formula VI wherein R₃, R₄, R₅ and A₁ are defined as above,may be prepared by reaction between compounds of formula V, wherein R₃is as defined in formula I, and compounds of formula VII, wherein R₄ andA₁ is defined in formula I, in suitable solvents that may include, forexample, mixture of acetic acid and 1,4-dioxane, usually upon heating attemperatures between room temperature and 200° C., preferably between40° C. to the boiling point of the reaction mixture, optionally undermicrowave heating conditions. Such processes have been describedpreviously, for example, in Tetrahedron 2017, 73, 750.

Compounds of formula V wherein R₃ is defined as above, may be preparedby reaction between compounds of formula IV, wherein R₂ is as defined informula I, and N,N-dimethylformamide dimethyl acetal (DMF-DMA), insuitable solvents that may include, for example, dichloromethane,usually upon heating at temperatures between room temperature and 200°C., preferably between 20° C. to the boiling point of the reactionmixture. Such processes have been described previously, for example, inTetrahedron 2017, 73, 750.

Compounds of formula IIa, wherein R₅ is as defined as in formula I, canbe prepared as shown in scheme 3;

As shown in scheme 3, compounds of formula IIa may be prepared byreaction between compounds of formula VIa, wherein R₃, R₄, R₅ and A₁ areas defined in formula I, and compounds of formula VIII, wherein R₁ isdefined in formula I, in suitable solvents that may include, forexample, acetonitrile or dioxane, in the presence of a suitable base,such as sodium, potassium or caesium carbonate (or sodium or potassiumhydrogen carbonate), usually upon heating at temperatures between roomtemperature and 200° C., preferably between 40° C. to the boiling pointof the reaction mixture, optionally under microwave heating conditions.

Compounds of formula VIa wherein R₃, R₄, R₅ and A₁ are defined as above,may be prepared by reaction between compounds of formula XI, wherein R₃and R₅ are as defined in formula I, and compounds of formula VII,wherein R₄ and A₁ are as defined in formula I, in suitable solvents thatmay include, for example, mixture of acetic acid and 1,4-dioxane,usually upon heating at temperatures between room temperature and 200°C., preferably between 40° C. to the boiling point of the reactionmixture, optionally under microwave heating conditions. Such processeshave been described previously, for example, in Tetrahedron 2017, 73,750.

Compounds of formula XI wherein R₃ and R₅ are defined as above, may beprepared by reaction between compounds of formula IX, wherein R₃ is asdefined in formula I, and compounds of formula X, wherein R₅ is asdefined in formula I, in suitable solvents that may include, forexample, DMF, in the presence of a suitable base, such as DIPEA uponheating at temperatures between room temperature and 200° C., preferablybetween 20° C. to the boiling point of the reaction mixture. Suchprocesses have been described previously, for example, in Journal ofOrganic Chemistry, 2011, 76, 1177.

Compounds of formula Ia, wherein R₁, R₂, R₃ R₄ and A₁ are defined asabove, can be further prepared by those skilled in the art as shown inscheme 4.

For example, compounds of formula I wherein, R₁, R₂, R₃, R₄ and A₁ aredefined as above, may be prepared by reaction between compounds offormula XIV wherein, R₁, R₂ and R₃ are defined as above, and compoundsof formula VII, wherein R₄ and A₁ are defined in formula I, in suitablesolvents that may include, for example, mixture of acetic acid and1,4-dioxane, usually upon heating at temperatures between roomtemperature and 200° C., preferably between 40° C. to the boiling pointof the reaction mixture, optionally under microwave heating conditions.Such processes have been described previously, for example, inTetrahedron 2017, 73, 750.

Compounds of formula XIV wherein, R₁, R₂ and R₃ are defined as above,may be prepared by reaction between compounds of formula XIII wherein,R₁, R₂ and R₃ are defined as above, and N,N-dimethylformamide dimethylacetal (DMF-DMA), in suitable solvents that may include, for example,dichloromethane, usually upon heating at temperatures between roomtemperature and 200° C., preferably between 40 to the boiling point ofthe reaction mixture. Such processes have been described previously, forexample, in Tetrahedron 2017, 73, 750, and US2016296501, preparation 7,page 29.

Compounds of formula XIII wherein, R₁, R₂ and R₃ are defined as above,may be prepared by reaction between compounds of formula XII, wherein R₁and R₃ are defined as above, and compounds of formula IIIa, wherein R₂and X₀ are defined as in Scheme 1, in suitable inert solvents that mayinclude, for example, pyridine, DMF, acetonitrile, CH₂Cl₂ or THF,optionally in the presence of a base, e.g. triethylamine or pyridine,usually upon heating at temperatures between room temperature and 200°C.

Compounds of formula XII, wherein R₁ and R₃ are defined as above, may beprepared by reaction between compounds of formula IV, wherein R₃ is asdefined in formula I, and compounds of formula VIII, wherein R₁ isdefined in formula I, in suitable solvents that may include, forexample, acetonitrile or dioxane, in the presence of a suitable base,such as sodium, potassium or cesium carbonate (or sodium or potassiumhydrogen carbonate), usually upon heating at temperatures between roomtemperature and 200° C., preferably between 40° C. to the boiling pointof the reaction mixture, optionally under microwave heating conditions.

Hydrazines of formula VII wherein A₁ is defined as above and R₄ is asdefined above are either commercially available or can be preparedaccording to well-known methods, or as shown in Scheme 5. Thus compoundsof formula XV, wherein A₁ is N or CH, and Xa1 is a leaving group such asCl, Br, F, I, OSO₂CF₃, or OSO₂CH₃ can be alkylated with a base, forexample caesium or potassium carbonate, in a solvent such asacetonitrile or DMF at temperatures between 20-80° C. with a compound offormula XIV, wherein Xa2 is a leaving group such as Cl, Br, F, I,OSO₂CF₃, or OSO₂CH₃, to give compounds of formula XIII wherein R₄, A₁and Xa1 are as previously defined. Such reactions are well known tothose skilled in the art and have been reported for example in see e.g.Med. Chem. Letts., 2017, 8(5), p543-548 and Bio. Med. Chem. Letts.,2017, 27(11), 2420-2423. Compounds of formula XIII can be treated withhydrazine in as suitable solvent for example, ethanol, aqueous dioxaneat temperatures 20-80° C. to give compounds of formula VII wherein R₄and A₁ are as previously described. Similar reactions have previouslybeen described for example in J. Med. Chem., 2018, 61(1), 207-223, andBio. Med. Chem. Letts., 2017, 27(21), 4858-4866. Compounds of formulaXIIIa wherein R₄ is CHF₂ can be prepared from compounds of formula XIIby treatment with a difluorocarbene source e.g. ClCF2CO2Na orCF2SO2OCHF2 in the presence of a base such as KOH, potassium carbonateand the like, in an inert solvent at temperatures between 20-80° C. Suchprocedures have been described for example in J. Fluor. Chem. 2017, 203,155, and US2013/0225552, page 128, and Org. Process Res. Dev., 2011, 15,721.

Compounds of formula I, wherein R₁, R₂, R₃, R₄, and A₁ are defined asabove, can also be prepared as shown in scheme 6

Compounds of formula I wherein R₁, R₂, R₃, R₄ and A₁ are as previouslydefined, can be prepared from compounds of formula XX, by treating withalkylating reagents of general formula XXI wherein Xa₄ is preferably Cl,Br, F, I, OSO₂CF₃, or OSO₂CH₃, in the presence of a base, such as sodiumhydride, K₂CO₃, or Cs₂CO₃, in an inert solvent such as THF, DMF, oracetonitrile, to give compounds of formula I. Such alkylation reactionsare well known to those skilled in the art.

Compounds of formula XX can also be obtained by Miyura borylation ofcompounds of formula XVI, followed by oxidation of the intermediate offormula XIX. The intermediate of formula XIX, wherein A₁, R₁, R₂, and R₃are defined as under formula I and BL₂ stands for a boronic acidderivative, preferably 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl, canbe obtained by treatment of compounds of formula XVII, wherein X_(a1) isCl, Br, I, or OTf, and X₁, R₁ and R₂ are as defined under formula I, ina palladium catalyzed reaction with bispinacol diborane (BPin)₂. Thisreaction, can be performed in an aprotic solvent, in presence of a base,preferably a weak base, such as potassium acetate KOAc, and Pd(dppf)Cl₂as a common catalyst for this type of reaction. The temperature of thereaction is preferably performed between 0° C. and the boiling point ofthe reaction mixture. The obtained intermediate of formula XIX can beconverted to compounds of formula XX by treatment with an oxidizingreagent, preferably hydrogen peroxide or the urea complex thereof.Compounds of formula XVII can also be converted to compounds of formulaXX by reaction with (E)-benzaldehyde oxime in an aprotic solvent such asacetonitrile or DMF, in the presence of a base, such as potassium orcesium carbonate, optionally in the presence of a palladium catalystsuch as RockPhos-G3-5aminobiphenyl)]palladium(II) methanesulfonate) attemperatures between 25-100° C. Such reactions are known in theliterature and have been described for example in Ang. Che. Int. Ed. 56,(16) 4478-4482, 2017. Compounds of formula XX so obtained are convertedto compounds of formula I by alkylation by methods well known to thoseskilled in the art and described above.

A further synthesis of compounds of formula I, particularly those inwhich R₄ is CF₃, namely compounds of formula Ic is described in scheme7:

According to scheme 7, compounds of formula XXII (Prepared as describedherein or in WO2017192385) can be treated in an inert solvent such asacetonitrile, a photo redox catalyst, such astris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate, underirradiation of blue LED light (15 W) in the presence of1-(trifluoromethoxy)pyridine-4-carbonitrile;1,1,1-trifluoro-N(trifluoromethylsulfonyl)methanesulfonamide, at roomtemperature. Such reactions have been described in the literature (seeAng. Chem., 2018, 57 (42), 13784-13789).

Compounds of formula III are known, for example3-(difluoromethyl)-5-(trifluoromethyl)benzoic acid CAS: [2248290-21-1],3-bromo-5-(trifluoromethyl)benzoic acid CAS: [328-67-6],3-iodo-5-(trifluoromethyl)benzoic acid, CAS: [28186-62-1] commerciallyavailable, or can be prepared by those skilled in the art. For examplesee also WO 2013/171712, WO 2012/117000, WO2017/192385. Some compoundsof formula III are novel and have been especially prepared to enablepreparation of compounds of formula I. Synthesis of such compounds isshown in scheme 8:

As shown in scheme 8, compounds of formula XXIII, wherein Z₀₁ ishalogen, preferably bromine or iodine, A₂ is nitrogen or methane, and Rais C₁-C₄alkyl, can be treated with a bipyridine copper reagent(bpy)CuSCF3, wherein bpy is bipyridyl, in an inert solvent such asacetonitrile or DMF, at temperatures between room temperature and 120°C., optionally under microwave heating, to give compounds of formulaXXIV, wherein A₂, and Ra are as previously defined. Such chemistry isknown and has been described in the literature, for example, in Angew.Chem. Int. Ed. 2013, 52, 1548-1552. A preferred reagent for thistransformation is (bpy)CuSCF₃ (CAS [1413732-47-4]). Compounds of formulaXXIV are converted to compounds of IIIb by ester hydrolysis, for examplereaction with a base e.g. Lithium, potassium, or sodium hydroxide, inwater optionally in the presence of a water miscible solvent such a THF,acetone, dioxane and the like. Such reactions are well known to thoseskilled in the art. Compounds of formula XXVI, wherein R₆ is C₁-C₃alkyl,and C₁-C₃haloalkyl, and Ra is C₁-C₄alkyl, can be prepared by reaction ofa compound of formula XXV with a compound of formula XXVII, wherein Xa₅is Cl, Br, F, I, OSO₂CF₃, or OSO₂CH₃, in the presence of a base, such assodium hydride, K₂CO₃, or Cs₂CO₃, in an inert solvent such as THF, DMF,or acetonitrile, to give compounds of formula XXVI. Compounds of formulaXXVI wherein R₆ is CHF₂ are prepared by treatment with in situ generateddifluorocarbene analogous to the procedures described for preparation ofXVIIa in scheme 5. Hydrolysis of compounds of formula XXVI to givecompounds of formula IIIc is as described vide supra.

Depending on the procedure or the reaction conditions, the reactants canbe reacted in the presence of a base. Examples of suitable bases arealkali metal or alkaline earth metal hydroxides, alkali metal oralkaline earth metal hydrides, alkali metal or alkaline earth metalamides, alkali metal or alkaline earth metal alkoxides, alkali metal oralkaline earth metal acetates, alkali metal or alkaline earth metalcarbonates, alkali metal or alkaline earth metal dialkylamides or alkalimetal or alkaline earth metal alkylsilylamides, alkylamines,alkylenediamines, free or N-alkylated saturated or unsaturatedcycloalkylamines, basic heterocycles, ammonium hydroxides andcarbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. If thereaction is carried out in the presence of a base, bases which areemployed in excess, such as triethylamine, pyridine, N-methylmorpholineor N,N-diethylaniline, may also act as solvents or diluents.

The reactions are advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between ambient temperature and approximately +80° C.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds of formula I can be prepared in a manner known perse. Thus, for example, acid addition salts of compounds of formula I areobtained by treatment with a suitable acid or a suitable ion exchangerreagent and salts with bases are obtained by treatment with a suitablebase or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in the customary mannerinto the free compounds I, acid addition salts, for example, bytreatment with a suitable basic compound or with a suitable ionexchanger reagent and salts with bases, for example, by treatment with asuitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in a manner known perse into other salts of compounds of formula I, acid addition salts, forexample, into other acid addition salts, for example by treatment of asalt of inorganic acid such as hydrochloride with a suitable metal saltsuch as a sodium, barium or silver salt, of an acid, for example withsilver acetate, in a suitable solvent in which an inorganic salt whichforms, for example silver chloride, is insoluble and thus precipitatesfrom the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds offormula I, which have salt-forming properties can be obtained in freeform or in the form of salts.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can be present inthe form of one of the isomers which are possible or as a mixture ofthese, for example in the form of pure isomers, such as antipodes and/ordiastereomers, or as isomer mixtures, such as enantiomer mixtures, forexample racemates, diastereomer mixtures or racemate mixtures, dependingon the number, absolute and relative configuration of asymmetric carbonatoms which occur in the molecule and/or depending on the configurationof non-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds of formula I, infree form or in salt form, which can be obtained depending on whichstarting materials and procedures have been chosen can be separated in aknown manner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl cellulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

N-oxides can be prepared by reacting a compound of the formula I with asuitable oxidizing agent, for example the H₂O₂/urea adduct in thepresence of an acid anhydride, e.g. trifluoroacetic anhydride. Suchoxidations are known from the literature, for example from J. Med.Chem., 32 (12), 2561-73, 1989 or WO 2000/15615.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can, if appropriate,also be obtained in the form of hydrates and/or include other solvents,for example those which may have been used for the crystallization ofcompounds which are present in solid form.

The compounds of formula I according to the following Tables A-1 toA-120 can be prepared according to the methods described above. Theexamples which follow are intended to illustrate the invention and showpreferred compounds of formula I, in the form of a compound of formulaIa.

Table A-1 provides 12 compounds A-1.001 to A-1.012 of formula Ia whereinR₁ is H, R₅ is H, R_(4a) is [5-(trifluoromethoxy)pyrimidin-2-yl] and R₂is as defined in table Z. For example, A-1.012 is

TABLE Z Substituent definitions of R₂: Index R₂ 1

2

3

4

5

6

7

8

9

10

11

12

Table A-2 provides 12 compounds A-2.001 to A-2.012 of formula Ia whereinR₁ is H, R₅ is H, R_(4a) is [5-(trifluoromethoxy)-2-pyridyl] and R₂ isas defined in table Z.Table A-3 provides 12 compounds A-3.001 to A-3.012 of formula Ia whereinR₁ is H, R₅ is H, R_(4a) is [5-(difluoromethoxy)pyrimidin-2-yl] and R₂is as defined in table Z.Table A-4 provides 12 compounds A-4.001 to A-4.012 of formula Ia whereinR₁ is H, R₅ is H, R_(4a) is [5-(difluoromethoxy)-2-pyridyl] and R₂ is asdefined in table Z.Table A-5 provides 12 compounds A-5.001 to A-5.012 of formula Ia whereinR₁ is H, R₅ is H, R_(4a) is [5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl]and R₂ is as defined in table Z.Table A-6 provides 12 compounds A-6.001 to A-6.012 of formula Ia whereinR₁ is H, R₅ is H, R_(4a) is [5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂is as defined in table Z.Table A-7 provides 12 compounds A-7.001 to A-7.012 of formula Ia whereinR₁ is H, R₅ is H, R_(4a) is [5-(2,2-difluoroethoxy)pyrimidin-2-yl] andR₂ is as defined in table Z.Table A-8 provides 12 compounds A-8.001 to A-8.012 of formula Ia whereinR₁ is H, R₅ is H, R_(4a) is [5-(2,2-difluoroethoxy)-2-pyridyl] and R₂ isas defined in table Z.Table A-9 provides 12 compounds A-9.001 to A-9.012 of formula Ia whereinR₁ is H, R₅ is H, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-10 provides 12 compounds A-10.001 to A-10.012 of formula Iawherein R₁ is H, R₅ is H, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-11 provides 12 compounds A-11.001 to A-11.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-12 provides 12 compounds A-12.001 to A-12.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is [5-(trifluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-13 provides 12 compounds A-13.001 to A-13.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-14 provides 12 compounds A-14.001 to A-14.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is [5-(difluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-15 provides 12 compounds A-15.001 to A-15.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-16 provides 12 compounds A-16.001 to A-16.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-17 provides 12 compounds A-17.001 to A-17.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-18 provides 12 compounds A-18.001 to A-18.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is [5-(2,2-difluoroethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-19 provides 12 compounds A-19.001 to A-19.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-20 provides 12 compounds A-20.001 to A-20.012 of formula Iawherein R₁ is H, R₅ is CH3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-21 provides 12 compounds A-21.001 to A-21.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-22 provides 12 compounds A-22.001 to A-22.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is [5-(trifluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-23 provides 12 compounds A-23.001 to A-23.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-24 provides 12 compounds A-24.001 to A-24.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is [5-(difluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-25 provides 12 compounds A-25.001 to A-25.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-26 provides 12 compounds A-26.001 to A-26.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-27 provides 12 compounds A-27.001 to A-27.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-28 provides 12 compounds A-28.001 to A-28.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is [5-(2,2-difluoroethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-29 provides 12 compounds A-29.001 to A-29.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-30 provides 12 compounds A-30.001 to A-30.012 of formula Iawherein R₁ is H, R₅ is Cyp, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-31 provides 12 compounds A-31.001 to A-31.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-32 provides 12 compounds A-32.001 to A-32.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is[5-(trifluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-33 provides 12 compounds A-33.001 to A-33.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-34 provides 12 compounds A-34.001 to A-34.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is [5-(difluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-35 provides 12 compounds A-35.001 to A-35.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-36 provides 12 compounds A-36.001 to A-36.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-37 provides 12 compounds A-37.001 to A-37.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-38 provides 12 compounds A-38.001 to A-38.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is[5-(2,2-difluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-39 provides 12 compounds A-39.001 to A-39.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-40 provides 12 compounds A-40.001 to A-40.012 of formula Iawherein R₁ is H, R₅ is CH2CF3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-41 provides 12 compounds A-41.001 to A-41.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-42 provides 12 compounds A-42.001 to A-42.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is [5-(trifluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-43 provides 12 compounds A-43.001 to A-43.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-44 provides 12 compounds A-44.001 to A-44.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is [5-(difluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-45 provides 12 compounds A-45.001 to A-45.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-46 provides 12 compounds A-46.001 to A-46.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-47 provides 12 compounds A-47.001 to A-47.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-48 provides 12 compounds A-48.001 to A-48.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is [5-(2,2-difluoroethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-49 provides 12 compounds A-49.001 to A-49.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-50 provides 12 compounds A-50.001 to A-50.012 of formula Iawherein R₁ is CH3, R₅ is H, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-51 provides 12 compounds A-51.001 to A-51.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-52 provides 12 compounds A-52.001 to A-52.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is [5-(trifluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-53 provides 12 compounds A-53.001 to A-53.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-54 provides 12 compounds A-54.001 to A-54.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is [5-(difluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-55 provides 12 compounds A-55.001 to A-55.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-56 provides 12 compounds A-56.001 to A-56.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-57 provides 12 compounds A-57.001 to A-57.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-58 provides 12 compounds A-58.001 to A-58.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is[5-(2,2-difluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-59 provides 12 compounds A-59.001 to A-59.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-60 provides 12 compounds A-60.001 to A-60.012 of formula Iawherein R₁ is CH3, R₅ is CH3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-61 provides 12 compounds A-61.001 to A-61.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-62 provides 12 compounds A-62.001 to A-62.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is [5-(trifluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-63 provides 12 compounds A-63.001 to A-63.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-64 provides 12 compounds A-64.001 to A-64.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is [5-(difluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-65 provides 12 compounds A-65.001 to A-65.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-66 provides 12 compounds A-66.001 to A-66.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-67 provides 12 compounds A-67.001 to A-67.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-68 provides 12 compounds A-68.001 to A-68.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is[5-(2,2-difluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-69 provides 12 compounds A-69.001 to A-69.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-70 provides 12 compounds A-70.001 to A-70.012 of formula Iawherein R₁ is CH3, R₅ is Cyp, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-71 provides 12 compounds A-71.001 to A-71.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-72 provides 12 compounds A-72.001 to A-72.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-(trifluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-73 provides 12 compounds A-73.001 to A-73.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-74 provides 12 compounds A-74.001 to A-74.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-(difluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-75 provides 12 compounds A-75.001 to A-75.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-76 provides 12 compounds A-76.001 to A-76.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-77 provides 12 compounds A-77.001 to A-77.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-78 provides 12 compounds A-78.001 to A-78.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-(2,2-difluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-79 provides 12 compounds A-79.001 to A-79.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-80 provides 12 compounds A-80.001 to A-80.012 of formula Iawherein R₁ is CH3, R₅ is CH2CF3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-81 provides 12 compounds A-81.001 to A-81.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-82 provides 12 compounds A-82.001 to A-82.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is[5-(trifluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-83 provides 12 compounds A-83.001 to A-83.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-84 provides 12 compounds A-84.001 to A-84.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is [5-(difluoromethoxy)-2-pyridyl]and R₂ is as defined in table Z.Table A-85 provides 12 compounds A-85.001 to A-85.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-86 provides 12 compounds A-86.001 to A-86.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-87 provides 12 compounds A-87.001 to A-87.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-88 provides 12 compounds A-88.001 to A-88.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is[5-(2,2-difluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-89 provides 12 compounds A-89.001 to A-89.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-90 provides 12 compounds A-90.001 to A-90.012 of formula Iawherein R₁ is CH2Cyp, R₅ is H, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-91 provides 12 compounds A-91.001 to A-91.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-92 provides 12 compounds A-92.001 to A-92.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-(trifluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-93 provides 12 compounds A-93.001 to A-93.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-94 provides 12 compounds A-94.001 to A-94.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-(difluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-95 provides 12 compounds A-95.001 to A-95.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-96 provides 12 compounds A-96.001 to A-96.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-97 provides 12 compounds A-97.001 to A-97.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-98 provides 12 compounds A-98.001 to A-98.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-(2,2-difluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-99 provides 12 compounds A-99.001 to A-99.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-100 provides 12 compounds A-100.001 to A-100.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-101 provides 12 compounds A-101.001 to A-101.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-102 provides 12 compounds A-102.001 to A-102.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-(trifluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-103 provides 12 compounds A-103.001 to A-103.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-104 provides 12 compounds A-104.001 to A-104.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-(difluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-105 provides 12 compounds A-105.001 to A-105.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-106 provides 12 compounds A-106.001 to A-106.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-107 provides 12 compounds A-107.001 to A-107.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-108 provides 12 compounds A-108.001 to A-108.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-(2,2-difluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-109 provides 12 compounds A-109.001 to A-109.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-110 provides 12 compounds A-110.001 to A-110.012 of formula Iawherein R₁ is CH2Cyp, R₅ is Cyp, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.Table A-111 provides 12 compounds A-111.001 to A-111.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-(trifluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-112 provides 12 compounds A-112.001 to A-112.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-(trifluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-113 provides 12 compounds A-113.001 to A-113.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-(difluoromethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-114 provides 12 compounds A-114.001 to A-114.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-(difluoromethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-115 provides 12 compounds A-115.001 to A-115.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-(2,2,2-trifluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in tableZ.Table A-116 provides 12 compounds A-116.001 to A-116.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-(2,2,2-trifluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-117 provides 12 compounds A-117.001 to A-117.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-(2,2-difluoroethoxy)pyrimidin-2-yl] and R₂ is as defined in table Z.Table A-118 provides 12 compounds A-118.001 to A-118.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-(2,2-difluoroethoxy)-2-pyridyl] and R₂ is as defined in table Z.Table A-119 provides 12 compounds A-119.001 to A-119.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]pyrimidin-2-yl] and R₂ is as definedin table Z.Table A-120 provides 12 compounds A-120.001 to A-120.012 of formula Iawherein R₁ is CH2Cyp, R₅ is CH2CF3, R_(4a) is[5-[(Z)-3,3,3-trifluoroprop-1-enoxy]-2-pyridyl] and R₂ is as defined intable Z.

Also made available are certain intermediate compounds of the amine offormula IIa

some of which are novel.

Specific examples of compounds of formula IIa are where (A) R₁ isCH₂Cyp, and R_(4a) is selected from J₁ to J₁₀; (B) R₁ is methyl, andR_(4a) is selected from J₁ to J₁₀; (C) R₁ is hydrogen, and R_(4a) isselected from J₁ to J₁₀.

Also made available are certain intermediate compounds of the amine offormula VIb, some of which are novel.

Specfic examples of compounds of formula VIb are where (A) R₃ is methyl,and R_(4a) is selected from J₁ to J₁₀, and R₅ is methyl; and (B) R₃ ismethyl, and R_(4a) is selected from J₁ to J₁₀, and R₅ is hydrogen,

Certain intermediate compounds of the amine of formulae XII and XIV aremade available herein, some of which are novel.

Specfic examples of compounds of formula XIII and XIV are where (A) R₁is CH₂Cyp, R₃ is methyl, and R₂ is as defined in table Z; (B) R₁ ismethyl, R₃ is methyl, and R₂ is as defined in table Z; (C) R₁ ishydrogen, R₃ is methyl, and R₂ is as defined in table Z.

Also made available are certain intermediate compounds of the amine offormula XXa

some of which are novel.

Specific examples of compounds of formula XXa are where (A) A₁ is N, R₁is CH₂Cyp and R₂ is as defined in table Z; (B) A₁ is N, R₁ is methyl andR₂ is as defined in table Z; (C) A₁ is N, R₁ is hydrogen and R₂ is asdefined in table Z; (D) A₁ is CH, R₁ is CH₂Cyp and R₂ is as defined intable Z; (E) A₁ is CH, R₁ is methyl and R₂ is as defined in table Z; and(F) A₁ is CH, R₁ is hydrogen and R₂ is as defined in table Z.

In further aspect, the present invention accordingly makes availablecompounds of formulae IIa, VIa, XIII, XIV and XXa, wherein in each case,as applicable, A₁, R₁, R₂, R₃, R₄ and R₅, are as defined for formula Iin the first aspect. Furthermore, the corresponding embodimentsillustrated for formula I also apply to the compounds of formulae IIa,VIa, XIII, XIV and XXa.

The compounds of formula I according to the invention are preventivelyand/or curatively valuable active ingredients in the field of pestcontrol, even at low rates of application, which have a very favorablebiocidal spectrum and are well tolerated by warm-blooded species, fishand plants. The active ingredients according to the invention actagainst all or individual developmental stages of normally sensitive,but also resistant, animal pests, such as insects or representatives ofthe order Acarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately oronly after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate.

Examples of the above mentioned animal pests are:

from the order Acarina, for example,Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro,Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobiaspp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemusspp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp.,Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora,Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalusspp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp,Tarsonemus spp. and Tetranychus spp.;from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;

from the order Coleoptera, for example,Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp.,Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis,Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp.,Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp.,Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp.,Heteronychus arator, Hypothenemus hampei, Lagria vilosa, LeptinotarsadecemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp,Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp.,Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophagaspp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatusaubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogaspp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebriospp., Tribolium spp. and Trogoderma spp.;from the order Diptera, for example,Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibiohortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp.,Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp,Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyzatripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyzaspp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp.,Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;from the order Hemiptera, for example,Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus,Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp.,Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma,Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus spp., Eurydemapulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus,Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic,Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans,Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp.,Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.,Thyanta spp, Triatoma spp., Vatiga illudens; Acyrthosium pisum, Adalgesspp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp,Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus,Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiellaspp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani,Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicorynebrassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp.,Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp,Cofana spectra, Cryptomyzus spp, Cicadulina spp, Coccus hesperidum,Dalbulus maidis, Dialeurodes spp, Diaphorina citri, Diuraphis noxia,Dysaphis spp, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae,Hyalopterus spp, Hyperomyzus pallidus, Idioscopus clypealis, Jacobiascalybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphiserysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp, Metcalfapruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.,Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piriMats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae,Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinusmaidis, Perkinsiella spp, Phorodon humuli, Phylloxera spp, Planococcusspp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelisseriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp.,Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera,Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp,Trialeurodes spp, Tridiscus sporoboli, Trionymus spp, Trioza erytreae,Unaspis citri, Zygina flammigera, Zyginidia scutellaris;from the order Hymenoptera, for example,Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae,Gilpinia polytoma, Hoplo-campa spp., Lasius spp., Monomorium pharaonis,Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp.and Vespa spp.;from the order Isoptera, for example,Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermesspp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsisgeminatefrom the order Lepidoptera, for example,Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrixthurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis,Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis,Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea,Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmeneacrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella,Euproctis spp., Euxoa spp., Feltia jaculiferia, Gra-pholita spp., Hedyanubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp,Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus,Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostegebifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestrabrassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp.,Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.,Panolis flammea, Papaipema nebris, Pectinophora gossypi-ela,Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaeaoperculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.,Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp.,Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate,Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tutaabsoluta, and Yponomeuta spp.; from the order Mallophaga, for example,Damalinea spp. and Trichodectes spp.;from the order Orthoptera, for example,Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscusspp, and Schistocerca spp.;from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;from the order Thysanoptera, for example,Calliothrips phaseoli, Frankliniella spp., Heliothrips spp,Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii,Sericothrips variabilis, Taeniothrips spp., Thrips spp;from the order Thysanura, for example, Lepisma saccharina.

In a further aspect, the invention may also relate to a method ofcontrolling damage to plant and parts thereof by plant parasiticnematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasiticnematodes), especially plant parasitic nematodes such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, Meloidogyne arenaria and other Meloidogyne species;cyst-forming nematodes, Globodera rostochiensis and other Globoderaspecies; Heterodera avenae, Heterodera glycines, Heterodera schachtii,Heterodera trifolii, and other Heterodera species; Seed gall nematodes,Anguina species; Stem and foliar nematodes, Aphelenchoides species;Sting nematodes, Belonolaimus longicaudatus and other Belonolaimusspecies; Pine nematodes, Bursaphelenchus xylophilus and otherBursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulbnematodes, Ditylenchus destructor, Ditylenchus dipsaci and otherDitylenchus species; Awl nematodes, Dolichodorus species; Spiralnematodes, Heliocotylenchus multicinctus and other Helicotylenchusspecies; Sheath and sheathoid nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; Lance nematodes,Hoploaimus species; false rootknot nematodes, Nacobbus species; Needlenematodes, Longidorus elongatus and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus, Rotylenchus reniformis and other Rotylenchus species;Scutellonema species; Stubby root nematodes, Trichodorus primitivus andother Trichodorus species, Paratrichodorus species; Stunt nematodes,Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species; Citrus nematodes, Tylenchulus species; Daggernematodes, Xiphinema species; and other plant parasitic nematodespecies, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp.,Melinius spp., Punctodera spp., and Quinisulcius spp.

The compounds of the invention may also have activity against themolluscs. Examples of which include, for example, Ampullariidae; Arion(A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae(Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina;Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum);Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H.itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix(H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L.maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M.sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp orjute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family and latex plants.

The compositions and/or methods of the present invention may be alsoused on any ornamental and/or vegetable crops, including flowers,shrubs, broad-leaved trees and evergreens.

For example the invention may be used on any of the following ornamentalspecies: Ageratum spp., Alonsoa spp., Anemone spp., Anisodonteacapsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp.(e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp.,Brachycome spp., Brassica spp. (ornamental), Calceolaria spp., Capsicumannuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemumspp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea,Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis,Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp.,Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp.,Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp.,Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp.,Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus,Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesiaspp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp.,Bellis spp., Pelargonium spp. (P. peltatum, P. Zonale), Viola spp.(pansy), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp.,Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp.,Ranunculus spp., Rhododendron spp., Rosa spp. (rose), Rudbeckia spp.,Saintpaulia spp., Salvia spp., Scaevola aemola, Schizanthuswisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp.,Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants.

For example the invention may be used on any of the following vegetablespecies: Allium spp. (A. sativum, A. cepa, A. oschaninii, A. Porrum, A.ascalonicum, A. fistulosum), Anthriscus cerefolium, Apium graveolus,Asparagus officinalis, Beta vulgarus, Brassica spp. (B. Oleracea, B.Pekinensis, B. rapa), Capsicum annuum, Cicer arietinum, Cichoriumendivia, Cichorum spp. (C. intybus, C. endivia), Citrillus lanatus,Cucumis spp. (C. sativus, C. melo), Cucurbita spp. (C. pepo, C. maxima),Cyanara spp. (C. scolymus, C. cardunculus), Daucus carota, Foeniculumvulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L.esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum,Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisumsativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salviaspp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea,Valerianella spp. (V. locusta, V. eriocarpa) and Vicia faba.

Preferred ornamental species include African violet, Begonia, Dahlia,Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster,Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum,Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia,Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper,tomato and cucumber.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca (preferably in vegetables, vineyards),Leptinotarsa (preferably in potatos) and Chilo supressalis (preferablyin rice).

The compounds of formula I are particularly suitable for control of

-   -   a pest of the order Hemiptera, for example, one or more of the        species Bemisia tabaci, Aphis craccivora, Myzus persicae,        Rhopalosiphum Padi, Nilaparvata lugens, and Euschistus heros        (preferably in vegetables, soybeans, and sugarcane);    -   a pest of the order Lepidoptera, for example, one or more of the        species Spodoptera littoralis, Spodoptera frugiperda, Plutella        xylostella, Cnaphalocrocis medinalis, Cydia pomonella,        Chrysodeixis includes, Chilo suppressalis, Elasmopalpus        lignosellus, Pseudoplusia includens, and Tuta absoluta        (preferably in vegetables and corn);    -   a pest of the order Thysanoptera, such as the family Thripidae,        for example, one or more of Thrips tabaci and Frankliniella        occidentalis (preferably in vegetables); and    -   soil pests (such as of the order Coleoptera), for example, the        species Diabrotica balteata, Agriotes spp. and Leptinotarsa        decemlineata (preferably in vegetables and corn).

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popilliae; or insecticidal proteins fromBacillus thuringiensis, such as 6-endotoxins, e.g. Cry1Ab, Cry1Ac,Cry1F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetativeinsecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; orinsecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for exampleVip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncatedtoxins and modified toxins. Hybrid toxins are produced recombinantly bya new combination of different domains of those proteins (see, forexample, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab,are known. In the case of modified toxins, one or more amino acids ofthe naturally occurring toxin are replaced. In such amino acidreplacements, preferably non-naturally present protease recognitionsequences are inserted into the toxin, such as, for example, in the caseof Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3Atoxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. CryI-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Crops may also be modified for enhanced resistance to fungal (forexample Fusarium, Anthracnose, or Phytophthora), bacterial (for examplePseudomonas) or viral (for example potato leafroll virus, tomato spottedwilt virus, cucumber mosaic virus) pathogens.

Crops also include those that have enhanced resistance to nematodes,such as the soybean cyst nematode.

Crops that are tolerance to abiotic stress include those that haveenhanced tolerance to drought, high salt, high temperature, chill,frost, or light radiation, for example through expression of NF-YB orother proteins known in the art.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Further areas of use of the compositions according to the invention arethe protection of stored goods and store rooms and the protection of rawmaterials, such as wood, textiles, floor coverings or buildings, andalso in the hygiene sector, especially the protection of humans,domestic animals and productive livestock against pests of the mentionedtype.

The present invention provides a compound of the first aspect for use intherapy. The present invention provides a compound of the first aspect,for use in controlling parasites in or on an animal. The presentinvention further provides a compound of the first aspect, for use incontrolling ectoparasites on an animal. The present invention furtherprovides a compound of the first aspect, for use in preventing and/ortreating diseases transmitted by ectoparasites.

The present invention provides the use of a compound of the firstaspect, for the manufacture of a medicament for controlling parasites inor on an animal. The present invention further provides the use of acompound of the first aspect, for the manufacture of a medicament forcontrolling ectoparasites on an animal. The present invention furtherprovides the use of a compound of the first aspect, for the manufactureof a medicament for preventing and/or treating diseases transmitted byectoparasites.

The present invention provides the use of a compound of the firstaspect, in controlling parasites in or on an animal. The presentinvention further provides the use of a compound of the first aspect, incontrolling ectoparasites on an animal.

The term “controlling” when used in context of parasites in or on ananimal refers to reducing the number of pests or parasites, eliminatingpests or parasites and/or preventing further pest or parasiteinfestation.

The term “treating” when used in context of parasites in or on an animalrefers to restraining, slowing, stopping or reversing the progression orseverity of an existing symptom or disease. The term “preventing” whenused in context of parasites in or on an animal refers to the avoidanceof a symptom or disease developing in the animal.

The term “animal” when used in context of parasites in or on an animalmay refer to a mammal and a non-mammal, such as a bird or fish. In thecase of a mammal, it may be a human or non-human mammal. Non-humanmammals include, but are not limited to, livestock animals and companionanimals. Livestock animals include, but are not limited to, cattle,camellids, pigs, sheep, goats and horses. Companion animals include, butare not limited to, dogs, cats and rabbits.

A “parasite” is a pest which lives in or on the host animal and benefitsby deriving nutrients at the host animal's expense. An “endoparasite” isa parasite which lives in the host animal. An “ectoparasite” is aparasite which lives on the host animal. Ectoparasites include, but arenot limited to, acari, insects and crustaceans (e.g. sea lice). TheAcari (or Acarina) sub-class comprises ticks and mites. Ticks include,but are not limited to, members of the following genera: Rhipicaphalus,for example, Rhipicaphalus (Boophilus) microplus and Rhipicephalussanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes;Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mitesinclude, but are not limited to, members of the following genera:Chorioptes, for example Chorioptes bovis; Psoroptes, for examplePsoroptes ovis; Cheyletiella; Dermanyssus; for example Dermanyssusgallinae; Ortnithonyssus; Demodex, for example Demodex canis; Sarcoptes,for example Sarcoptes scabiei; and Psorergates. Insects include, but arenot limited to, members of the orders: Siphonaptera, Diptera,Phthiraptera, Lepidoptera, Coleoptera and Homoptera. Members of theSiphonaptera order include, but are not limited to, Ctenocephalidesfelis and Ctenocephatides canis. Members of the Diptera order include,but are not limited to, Musca spp.; bot fly, for example Gasterophilusintestinalis and Oestrus ovis; biting flies; horse flies, for exampleHaematopota spp. and Tabunus spp.; Haematobia, for example Haematobiairritans; Stomoxys; Lucilia; midges; and mosquitoes. Members of thePhthiraptera class include, but are not limited to, blood sucking liceand chewing lice, for example Bovicola Ovis and Bovicola Bovis.

The term “effective amount” when used in context of parasites in or onan animal refers to the amount or dose of the compound of the invention,or a salt thereof, which, upon single or multiple dose administration tothe animal, provides the desired effect in or on the animal. Theeffective amount can be readily determined by the attendingdiagnostician, as one skilled in the art, by the use of known techniquesand by observing results obtained under analogous circumstances. Indetermining the effective amount a number of factors are considered bythe attending diagnostician, including, but not limited to: the speciesof mammal; its size, age, and general health; the parasite to becontrolled and the degree of infestation; the specific disease ordisorder involved; the degree of or involvement or the severity of thedisease or disorder; the response of the individual; the particularcompound administered; the mode of administration; the bioavailabilitycharacteristics of the preparation administered; the dose regimenselected; the use of concomitant medication; and other relevantcircumstances.

The compounds of the invention may be administered to the animal by anyroute which has the desired effect including, but not limited totopically, orally, parenterally and subcutaneously. Topicaladministration is preferred. Formulations suitable for topicaladministration include, for example, solutions, emulsions andsuspensions and may take the form of a pour-on, spot-on, spray-on, sprayrace or dip. In the alternative, the compounds of the invention may beadministered by means of an ear tag or collar.

Salt forms of the compounds of the invention include bothpharmaceutically acceptable salts and veterinary acceptable salts, whichcan be different to agrochemically acceptable salts. Pharmaceuticallyand veterinary acceptable salts and common methodology for preparingthem are well known in the art. See, for example, Gould, P. L., “Saltselection for basic drugs”, International Journal of Pharmaceutics, 33:201-217 (1986); Bastin, R. J., et al. “Salt Selection and OptimizationProcedures for Pharmaceutical New Chemical Entities”, Organic ProcessResearch and Development, 4: 427-435 (2000); and Berge, S. M., et al.,“Pharmaceutical Salts”, Journal of Pharmaceutical Sciences, 66: 1-19,(1977). One skilled in the art of synthesis will appreciate that thecompounds of the invention are readily converted to and may be isolatedas a salt, such as a hydrochloride salt, using techniques and conditionswell known to one of ordinary skill in the art. In addition, one skilledin the art of synthesis will appreciate that the compounds of theinvention are readily converted to and may be isolated as thecorresponding free base from the corresponding salt.

The present invention also provides a method for controlling pests (suchas mosquitoes and other disease vectors; see alsohttp://www.who.int/malaria/vector_control/irs/en/). In one embodiment,the method for controlling pests comprises applying the compositions ofthe invention to the target pests, to their locus or to a surface orsubstrate by brushing, rolling, spraying, spreading or dipping. By wayof example, an IRS (indoor residual spraying) application of a surfacesuch as a wall, ceiling or floor surface is contemplated by the methodof the invention. In another embodiment, it is contemplated to applysuch compositions to a substrate such as non-woven or a fabric materialin the form of (or which can be used in the manufacture of) netting,clothing, bedding, curtains and tents.

In one embodiment, the method for controlling such pests comprisesapplying a pesticidally effective amount of the compositions of theinvention to the target pests, to their locus, or to a surface orsubstrate so as to provide effective residual pesticidal activity on thesurface or substrate. Such application may be made by brushing, rolling,spraying, spreading or dipping the pesticidal composition of theinvention. By way of example, an IRS application of a surface such as awall, ceiling or floor surface is contemplated by the method of theinvention so as to provide effective residual pesticidal activity on thesurface. In another embodiment, it is contemplated to apply suchcompositions for residual control of pests on a substrate such as afabric material in the form of (or which can be used in the manufactureof) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may bemade of natural fibres such as cotton, raffia, jute, flax, sisal,hessian, or wool, or synthetic fibres such as polyamide, polyester,polypropylene, polyacrylonitrile or the like. The polyesters areparticularly suitable. The methods of textile treatment are known, e.g.WO 2008/151984, WO 2003/034823, U.S. Pat. No. 5,631,072, WO 2005/64072,WO2006/128870, EP 1724392, WO 2005113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention arethe field of tree injection/trunk treatment for all ornamental trees aswell all sort of fruit and nut trees.

In the field of tree injection/trunk treatment, the compounds accordingto the present invention are especially suitable against wood-boringinsects from the order Lepidoptera as mentioned above and from the orderColeoptera, especially against woodborers listed in the following tablesA and B:

TABLE A Examples of exotic woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus planipennis AshCerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandruscrassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperdaConifers

TABLE B Examples of native woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus anxius Birch Agriluspolitus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilusvittaticolllis Apple, Pear, Cranberry, Serviceberry, HawthornChrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry,Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut,Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum,Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texaniacampestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplarCerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak,Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytusacuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Easternhophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust,Honeylocust, Yellow-poplar, Chestnut, Osage-orange, Sassafras, Lilac,Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood,Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleafhackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant,Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood,Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, MulberryOncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood,Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit treesSaperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory,Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak,Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, ElmDendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wildcherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut,Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, PinePhloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry,Mountain-ash Pseudopityophthorus pruinosus Oak, American beech, Blackcherry, Chickasaw plum, Chestnut, Maple, Hickory, Hornbeam, HophornbeamSesiidae Paranthrene simulans Oak, American chestnut Sanninauroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine,Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum,Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedonscitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Blackcherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark,Bayberry Vitacea polistiformis Grape

The present invention may be also used to control any insect pests thatmay be present in turfgrass, including for example beetles,caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites,mole crickets, scales, mealybugs, ticks, spittlebugs, southern chinchbugs and white grubs. The present invention may be used to controlinsect pests at various stages of their life cycle, including eggs,larvae, nymphs and adults.

In particular, the present invention may be used to control insect peststhat feed on the roots of turfgrass including white grubs (such asCyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp.(e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green Junebeetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica),Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Blackturfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic gardenbeetle, M. castanea) and Tomarus spp.), ground pearls (Margarodes spp.),mole crickets (tawny, southern, and short-winged; Scapteriscus spp.,Gryllotalpa africana) and leatherjackets (European crane fly, Tipulaspp.).

The present invention may also be used to control insect pests ofturfgrass that are thatch dwelling, including armyworms (such as fallarmyworm Spodoptera frugiperda, and common armyworm Pseudaletiaunipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatusverstitus and S. parvulus), and sod webworms (such as Crambus spp. andthe tropical sod webworm, Herpetogramma phaeopteralis).

The present invention may also be used to control insect pests ofturfgrass that live above the ground and feed on the turfgrass leaves,including chinch bugs (such as southern chinch bugs, Blissus insularis),Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug(Antonina graminis), two-lined spittlebug (Propsapia bicincta),leafhoppers, cutworms (Noctuidae family), and greenbugs.

The present invention may also be used to control other pests ofturfgrass such as red imported fire ants (Solenopsis invicta) thatcreate ant mounds in turf.

In the hygiene sector, the compositions according to the invention areactive against ectoparasites such as hard ticks, soft ticks, mangemites, harvest mites, flies (biting and licking), parasitic fly larvae,lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorusspp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compositions according to the invention are also suitable forprotecting against insect infestation in the case of materials such aswood, textiles, plastics, adhesives, glues, paints, paper and card,leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirexjuvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharina. Thecompounds of formulae I, and I′a, or salts thereof, are especiallysuitable for controlling one or more pests selected from the family:Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae,Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae,Meloidogynidae, and Heteroderidae. In a preferred embodiment of eachaspect, a compound TX (where the abbreviation “TX” means “one compoundselected from the compounds defined in the Tables A-1 to A-120 and TableP”) controls one or more of pests selected from the family: Noctuidae,Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae,Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, andHeteroderidae.

The compounds of formulae I, and I′a, or salts thereof, are especiallysuitable for controlling one or more of pests selected from the genus:Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp, Euschistusspp, Cydia spp, Nilaparvata spp, Myzus spp, Aphis spp, Diabrotica spp,Rhopalosiphum spp, Pseudoplusia spp and Chilo spp. In a preferredembodiment of each aspect, a compound TX (where the abbreviation “TX”means “one compound selected from the compounds defined in the TablesA-1 to A-120 and Table P”) controls one or more of pests selected fromthe genus: Spodoptera spp, Plutella spp, Frankliniella spp, Thrips spp,Euschistus spp, Cydia spp, Nilaparvata spp, Myzus spp, Aphis spp,Diabrotica spp, Rhopalosiphum spp, Pseudoplusia spp and Chilo spp.

The compounds of formulae I, and I′a, or salts thereof, are especiallysuitable for controlling one or more of Spodoptera littoralis, Plutellaxylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros,Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixisincludens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi,and Chilo suppressalis.

In a preferred embodiment of each aspect, a compound TX (where theabbreviation “TX” means “one compound selected from the compoundsdefined in the Tables A-1 to A-120 and Table P”) controls one or more ofSpodoptera littoralis, Plutella xylostella, Frankliniella occidentalis,Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens,Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabroticabalteata, Rhopalosiphum Padia, and Chilo Suppressalis, such asSpodoptera littoralis+TX, Plutella xylostella+TX; Frankliniellaoccidentalis+TX, Thrips tabaci+TX, Euschistus heros+TX, Cydiapomonella+TX, Nilaparvata lugens+TX, Myzus persicae+TX, Chrysodeixisincludens+TX, Aphis craccivora+TX, Diabrotica balteata+TX, RhopalosiphumPadi+TX, and Chilo suppressalis+TX.

In an embodiment, of each aspect, one compound selected from thecompounds defined in the Tables A-1 to A-120 and Table P is suitable forcontrolling Spodoptera littoralis, Plutella xylostella, Frankliniellaoccidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella,Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphiscraccivora, Diabrotica balteata, Rhopalosiphum Padia, and ChiloSuppressalis in cotton, vegetable, maize, cereal, rice and soya crops.

In an embodiment, one compound from selected from the compounds definedin the Tables A-1 to A-120 and Table P is suitable for controllingMamestra (preferably in vegetables), Cydia pomonella (preferably inapples), Empoasca (preferably in vegetables, vineyards), Leptinotarsa(preferably in potatos) and Chilo supressalis (preferably in rice).

Compounds according to the invention may possess any number of benefitsincluding, inter alia, advantageous levels of biological activity forprotecting plants against insects or superior properties for use asagrochemical active ingredients (for example, greater biologicalactivity, an advantageous spectrum of activity, an increased safetyprofile (against non-target organisms above and below ground (such asfish, birds and bees), improved physico-chemical properties, orincreased biodegradability). In particular, it has been surprisinglyfound that certain compounds of formula I may show an advantageoussafety profile with respect to non-target arthropods, in particularpollinators such as honey bees, solitary bees, and bumble bees. Mostparticularly, Apis mellifera.

The compounds according to the invention can be used as pesticidalagents in unmodified form, but they are generally formulated intocompositions in various ways using formulation adjuvants, such ascarriers, solvents and surface-active substances. The formulations canbe in various physical forms, e.g. in the form of dusting powders, gels,wettable powders, water-dispersible granules, water-dispersible tablets,effervescent pellets, emulsifiable concentrates, microemulsifiableconcentrates, oil-in-water emulsions, oil-flowables, aqueousdispersions, oily dispersions, suspo-emulsions, capsule suspensions,emulsifiable granules, soluble liquids, water-soluble concentrates (withwater or a water-miscible organic solvent as carrier), impregnatedpolymer films or in other forms known e.g. from the Manual onDevelopment and Use of FAO and WHO Specifications for Pesticides, UnitedNations, First Edition, Second Revision (2010). Such formulations caneither be used directly or diluted prior to use. The dilutions can bemade, for example, with water, liquid fertilisers, micronutrients,biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredientwith the formulation adjuvants in order to obtain compositions in theform of finely divided solids, granules, solutions, dispersions oremulsions. The active ingredients can also be formulated with otheradjuvants, such as finely divided solids, mineral oils, oils ofvegetable or animal origin, modified oils of vegetable or animal origin,organic solvents, water, surface-active substances or combinationsthereof.

The active ingredients can also be contained in very fine microcapsules.Microcapsules contain the active ingredients in a porous carrier. Thisenables the active ingredients to be released into the environment incontrolled amounts (e.g. slow-release). Microcapsules usually have adiameter of from 0.1 to 500 microns. They contain active ingredients inan amount of about from 25 to 95% by weight of the capsule weight. Theactive ingredients can be in the form of a monolithic solid, in the formof fine particles in solid or liquid dispersion or in the form of asuitable solution. The encapsulating membranes can comprise, forexample, natural or synthetic rubbers, cellulose, styrene/butadienecopolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides,polyureas, polyurethane or chemically modified polymers and starchxanthates or other polymers that are known to the person skilled in theart. Alternatively, very fine microcapsules can be formed in which theactive ingredient is contained in the form of finely divided particlesin a solid matrix of base substance, but the microcapsules are notthemselves encapsulated.

The formulation adjuvants that are suitable for the preparation of thecompositions according to the invention are known per se. As liquidcarriers there may be used: water, toluene, xylene, petroleum ether,vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acidanhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkylesters of acetic acid, diacetone alcohol, 1,2-dichloropropane,diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycolabietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methylether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,ethyl acetate, 2-ethylhexanol, ethylene carbonate,1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyllactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycolmethyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glyceroldiacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,isopropyl myristate, lactic acid, laurylamine, mesityl oxide,methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyllaurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene,n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleicacid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid,propyl lactate, propylene carbonate, propylene glycol, propylene glycolmethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol,xylenesulfonic acid, paraffin, mineral oil, trichloroethylene,perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propyleneglycol methyl ether, diethylene glycol methyl ether, methanol, ethanol,isopropanol, and alcohols of higher molecular weight, such as amylalcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol,propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide,pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone,calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks,wheat flour, soybean flour, pumice, wood flour, ground walnut shells,lignin and similar substances.

A large number of surface-active substances can advantageously be usedin both solid and liquid formulations, especially in those formulationswhich can be diluted with a carrier prior to use. Surface-activesubstances may be anionic, cationic, non-ionic or polymeric and they canbe used as emulsifiers, wetting agents or suspending agents or for otherpurposes. Typical surface-active substances include, for example, saltsof alkyl sulfates, such as diethanolammonium lauryl sulfate; salts ofalkylarylsulfonates, such as calcium dodecylbenzenesulfonate;alkylphenol/alkylene oxide addition products, such as nonylphenolethoxylate; alcohol/alkylene oxide addition products, such astridecylalcohol ethoxylate; soaps, such as sodium stearate; salts ofalkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate;dialkyl esters of sulfosuccinate salts, such as sodiumdi(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitololeate; quaternary amines, such as lauryltrimethylammonium chloride,polyethylene glycol esters of fatty acids, such as polyethylene glycolstearate; block copolymers of ethylene oxide and propylene oxide; andsalts of mono- and di-alkylphosphate esters; and also further substancesdescribed e.g. in McCutcheon's Detergents and Emulsifiers Annual, MCPublishing Corp., Ridgewood N.J. (1981).

Further adjuvants that can be used in pesticidal formulations includecrystallisation inhibitors, viscosity modifiers, suspending agents,dyes, anti-oxidants, foaming agents, light absorbers, mixingauxiliaries, antifoams, complexing agents, neutralising or pH-modifyingsubstances and buffers, corrosion inhibitors, fragrances, wettingagents, take-up enhancers, micronutrients, plasticisers, glidants,lubricants, dispersants, thickeners, antifreezes, microbicides, andliquid and solid fertilisers.

The compositions according to the invention can include an additivecomprising an oil of vegetable or animal origin, a mineral oil, alkylesters of such oils or mixtures of such oils and oil derivatives. Theamount of oil additive in the composition according to the invention isgenerally from 0.01 to 10%, based on the mixture to be applied. Forexample, the oil additive can be added to a spray tank in the desiredconcentration after a spray mixture has been prepared. Preferred oiladditives comprise mineral oils or an oil of vegetable origin, forexample rapeseed oil, olive oil or sunflower oil, emulsified vegetableoil, alkyl esters of oils of vegetable origin, for example the methylderivatives, or an oil of animal origin, such as fish oil or beeftallow. Preferred oil additives comprise alkyl esters of C₈-C₂₂ fattyacids, especially the methyl derivatives of C₁₂-C₁₈ fatty acids, forexample the methyl esters of lauric acid, palmitic acid and oleic acid(methyl laurate, methyl palmitate and methyl oleate, respectively). Manyoil derivatives are known from the Compendium of Herbicide Adjuvants,10^(th) Edition, Southern Illinois University, 2010.

The inventive compositions generally comprise from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, of compounds of the presentinvention and from 1 to 99.9% by weight of a formulation adjuvant whichpreferably includes from 0 to 25% by weight of a surface-activesubstance. Whereas commercial products may preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The rates of application vary within wide limits and depend on thenature of the soil, the method of application, the crop plant, the pestto be controlled, the prevailing climatic conditions, and other factorsgoverned by the method of application, the time of application and thetarget crop. As a general guideline compounds may be applied at a rateof from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Preferred formulations can have the following compositions (weight %):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 60 to 90%surface-active agent: 1 to 30%, preferably 5 to 20%liquid carrier: 1 to 80%, preferably 1 to 35%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 5%solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%water: 94 to 24%, preferably 88 to 30%surface-active agent: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%surface-active agent: 0.5 to 20%, preferably 1 to 15%solid carrier: 5 to 95%, preferably 15 to 90%

Granules:

active ingredient: 0.1 to 30%, preferably 0.1 to 15%solid carrier: 99.5 to 70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, theinvention.

Wettable powders a) b) c) active ingredients 25%  50% 75% sodiumlignosulfonate 5%  5% — sodium lauryl sulfate 3% —  5% sodiumdiisobutylnaphthalenesulfonate —  6% 10% phenol polyethylene glycolether (7-8 mol of —  2% — ethylene oxide) highly dispersed silicic acid5% 10% 10% Kaolin 62%  27% —

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording wettable powders thatcan be diluted with water to give suspensions of the desiredconcentration.

Powders for dry seed treatment a) b) c) active ingredients 25% 50% 75%light mineral oil  5%  5%  5% highly dispersed silicic acid  5%  5% —Kaolin 65% 40% — Talcum — 20%

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording powders that can beused directly for seed treatment.

Emulsifiable concentrate active ingredients 10% octylphenol polyethyleneglycol ether (4-5 mol of ethylene  3% oxide) calciumdodecylbenzenesulfonate  3% castor oil polyglycol ether (35 mol ofethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredients  5%  6%  4% Talcum 95% — — Kaolin —94% — mineral filler — — 96%

Ready-for-use dusts are obtained by mixing the combination with thecarrier and grinding the mixture in a suitable mill. Such powders canalso be used for dry dressings for seed.

Extruder granules Active ingredients 15% sodium lignosulfonate  2%carboxymethylcellulose  1% Kaolin 82%

The combination is mixed and ground with the adjuvants, and the mixtureis moistened with water. The mixture is extruded and then dried in astream of air.

Coated granules Active ingredients 8% polyethylene glycol (mol. wt. 200)3% Kaolin 89% 

The finely ground combination is uniformly applied, in a mixer, to thekaolin moistened with polyethylene glycol. Non-dusty coated granules areobtained in this manner.

Suspension Concentrate

active ingredients 40% propylene glycol 10% nonylphenol polyethyleneglycol ether (15 mol of ethylene oxide)  6% Sodium lignosulfonate 10%carboxymethylcellulose  1% silicone oil (in the form of a 75% emulsionin water)  1% Water 32%

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Flowable Concentrate for Seed Treatment

active ingredients 40%  propylene glycol 5% copolymer butanol PO/EO 2%Tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (inthe form of a 20% solution 0.5%  in water) monoazo-pigment calcium salt5% Silicone oil (in the form of a 75% emulsion in water) 0.2%  Water45.3%  

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Slow Release Capsule Suspension

28 parts of the combination are mixed with 2 parts of an aromaticsolvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed. The obtainedcapsule suspension is stabilized by adding 0.25 parts of a thickener and3 parts of a dispersing agent. The capsule suspension formulationcontains 28% of the active ingredients. The medium capsule diameter is8-15 microns. The resulting formulation is applied to seeds as anaqueous suspension in an apparatus suitable for that purpose.

Formulation types include an emulsion concentrate (EC), a suspensionconcentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), awater dispersible granule (WG), an emulsifiable granule (EG), anemulsion, water in oil (EO), an emulsion, oil in water (EW), amicro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable(OF), an oil miscible liquid (OL), a soluble concentrate (SL), anultra-low volume suspension (SU), an ultra-low volume liquid (UL), atechnical concentrate (TK), a dispersible concentrate (DC), a wettablepowder (WP), a soluble granule (SG) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

PREPARATORY EXAMPLES

“Mp” means melting point in ° C. Free radicals represent methyl groups.1H NMR measurements were recorded on a Brucker 400 MHz spectrometer,chemical shifts are given in ppm relevant to a TMS standard. Spectrameasured in deuterated solvents as indicated. Either one of the LCMSmethods below was used to characterize the compounds. The characteristicLCMS values obtained for each compound were the retention time (“Rt”,recorded in minutes) and the measured molecular ion (M+H)*.

LC-MS Methods:

Method 1: Spectra were recorded on a Mass Spectrometer from Waters (SQD,SQDII Single quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions, Capillary: 3.00 kV, Conerange: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2min; Flow (ml/min) 0.85.

Method 2: Spectra were recorded on a Mass Spectrometer from Waters (SQD,SQDII Single quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 650l/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 2.7min; Flow (ml/min) 0.85.

Example 1: Synthesis ofN-[1-[2-[5-(trifluoromethoxy)pyrimidin-2-yl]-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide(Compound P1)

In a dry vial, under Argon,N-[1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamideprepared as described in WO 2017192385 (0.5478 g, 1.273 mmol),1-(trifluoromethoxy)pyridine-4-carbonitrile;1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (0.2 g,0.4244 mmol) and Tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate(0.01824 g, 0.02122 mmol) were dissolved in Acetonitrile (12 mL). Thebright red solution was stirred at room temperature under irradiation ofblue LED light (15 W). The reaction was monitored by LC-MS and TLC.After 2 hours, the solvent was evaporated and the crude was purified bychromatography over silica gel then by reverse phase to affordN-[1-[2-[5-(trifluoromethoxy)pyrimidin-2-yl]-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide.

1H NMR (400 MHz, Chloroform) δ ppm 1.76 (d, J=6.60 Hz, 3H) 6.37-6.48 (m,1H) 7.44-7.50 (m, 1H) 8.05 (s, 1H) 8.11 (s, 1H) 8.28 (s, 2H) 8.82-8.93(m, 2H).

LC-MS (Method 1): 515 (M+H), Rt: 1.06 min.

Example 2: Synthesis ofN-[1-[2-[5-(2,2,2-trifluoroethoxy)-2-pyridyl]-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide(Compound P8)

Step 1: Preparation ofN-[2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-3,5-bis(trifluoromethyl)benzamide

N-(2-amino-1-methyl-2-oxo-ethyl)-3,5-bis(trifluoromethyl)benzamide(preparation described in WO 2017192385 14.67 g, 44.70 mmol) was takenin dichloromethane (90 mL) under argon to give a pale yellow suspension.The N,N-dimethylformamide dimethyl acetal (9.48 mL, 67.05 mmol) wasadded dropwise. The resulting mixture was stirred for 18 hours at roomtemperature and then the solvent was evaporated to affordN-[2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-3,5-bis(trifluoromethyl)benzamideas a crude used in the next step without further purification.

LC-MS (Method 1): 384 [M+H], RT: 0.79 min

Step 2: Preparation ofN-[1-[2-(5-bromo-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide

N-[2-[(E)-dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-3,5-bis(trifluoromethyl)benzamide(8.565 g, 22.35 mmol) was dissolved in 1,4-dioxane (45 mL) and aceticacid (45 mL) under argon. 5-bromo-2-hydrazinopyridine (CAS: 77992-44-0,5.198 g, 26.81 mmol) was added in several portions and the resultingmixture was stirred for 3 hours at 50° C. The solvent was evaporatedunder vacuum at 60° C. The residue obtained was diluted with aqueoussaturated NaHCO3 and ethyl acetate. The aqueous phase was washed twicewith ethyl acetate. The organic layers were combined, washed once withwater, once with brine, dried over anhydrous sodium thiosulfate,filtered and concentrated under vacuum at 60° C. The crude was purifiedby chromatography over silica gel to affordN-[1-[2-(5-bromo-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide.

1H NMR (400 MHz, CDCl3) δ ppm 1.74 (d, J=6.60 Hz, 3H) 6.34-6.44 (m, 1H)7.80 (br d, J=8.07 Hz, 1H) 7.92 (d, J=8.44 Hz, 1H) 8.01 (s, 1H) 8.03 (s,1H) 8.07 (dd, J=8.62, 2.38 Hz, 1H) 8.30 (s, 2H) 8.64-8.68 (m, 1H)

LC-MS (Method 1): 510 [M+H], RT: 1.13 min

Step 3: Preparation ofN-[1-[2-(5-hydroxy-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide

N-[1-[2-(5-bromo-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide(0.250 g, 0.492 mmol), benzaldoxime (0.0791 g, 0.0712 mL, 0.640 mmol)and cesium carbonate (0.356 g, 1.08 mmol) were dissolved inN,N-dimethylformamide (0.984 mL) under argon. The resulting suspensionwas degassed for 5 minutes with argon. Then RockPhos Pd G3 (0.0124 g,0.0300) was added. The resulting dark brown suspension was stirred at80° C. for 3 days. After cooling down at room temperature,dichloromethane and water were added. This biphasic suspension wasfiltered through Celite and the two resulting phases of the filtratewere separated. The aqueous phase was washed once with dichloromethane.Combined organic layers were joined, washed once with saturated aqueousNH₄Cl, dried over anhydrous Na2SO4, filtered and evaporated under vacuumat 60° C. The crude was purified by chromatography over silica gel toaffordN-[1-[2-(5-hydroxy-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide.1H NMR (400 MHz, DMSO) δ ppm 1.62 (d, J=6.97 Hz, 3H) 3.34 (s, 4H) 5.86(t, J=6.97 Hz, 1H) 7.40 (dd, J=8.80, 2.93 Hz, 1H) 7.62 (d, J=8.80 Hz,1H) 8.03 (d, J=2.93 Hz, 1H) 8.08 (s, 1H) 8.31 (s, 1H) 8.40 (s, 2H) 9.49(d, J=7.34 Hz, 1H) 10.39 (s, 1H)

LC-MS (Method 1): 528 [M+H], Rt: 1.13 min

Step 4: Preparation ofN-[1-[2-[5-(2,2,2-trifluoroethoxy)-2-pyridyl]-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide

Cesium carbonate (0.056 g, 0.17 mmol) followed by the2,2,2-trifluoroethyltrifluoromethanesulfonate (0.016 mL, 0.11 mmol) wereadded to a suspension ofN-[1-[2-(5-hydroxy-2-pyridyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide(0.038 g, 0.085 mmol) in acetonitrile (0.85 mL) under argon. Theresulting mixture was stirred 1 hour at room temperature and then waspoured into water. The aqueous layer was extracted twice with ethylacetate. Organic layers were joined, washed once with brine, dried overanhydrous sodium sulfate, filtered and evaporated under vacuum at 60°.The crude was purified by chromatography over silica gel to affordN-[1-[2-[5-(2,2,2-trifluoroethoxy)-2-pyridyl]-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide.

1H NMR (400 MHz, Chloroform) δ ppm 1.72 (d, J=6.60 Hz, 3H) 4.51 (q,J=8.07 Hz, 2H) 6.25-6.41 (m, 1H) 7.55 (dd, J=9.17, 2.93 Hz, 1H)7.87-7.94 (m, 1H) 7.96 (d, J=8.80 Hz, 1H) 7.99 (s, 1H) 8.03 (s, 1H)8.24-8.37 (m, 3H)

LC-MS (Method 1): 528 [M+H], Rt: 1.13 min

RT [M + H] Meth- Entry IUPAC name STRUCTURE (min) (measured) od MP ° C.P1 N-[1-[2-[5- (trifluoromethoxy) pyrimidin-2- yl]-1,2,4-triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide

1.06 515 1 P2 N-[1-[2-[5-(1,1,2,2,2- pentafluoroethoxy)pyrimidin-2-yl]-1,2,4- triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl)benzamide

P3 N-[1-[2-[5- (difluoromethoxy) pyrimidin-2- yl]-1,2,4-triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide

1.04 497 1 163- 164 P4 N-[1-[2-[5-(2,2,2- trifluoroethoxy)pyrimidin-2-yl]-1,2,4- triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl)benzamide

1.07 529 1 162- 163 P5 N-[1-[2-[5-(2,2- difluoroethoxy)pyrimidin-2-yl]-1,2,4-triazol- 3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide

1.03 511 1 190- 193 P6 N-[1-[2-[5- (trifluoromethoxy)- 2-pyridyl]-1,2,4-triazol-3- yl]ethyl]-3,5- bis(trifluoromethyl) benzamide

1.18 514 1 P7 N-[(1S)-1-[2-[5- (trifluoromethoxy) pyrimidin-2-yl]-1,2,4-triazol-3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide

1.06 515 1 P8 N-[1-[2-[5-(2,2,2- trifluoroethoxy)-2-pyridyl]-1,2,4-triazol- 3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide

1.13 528 1 P9 N-[1-[2-[5-(2,2- difluoroethoxy)-2-pyridyl]-1,2,4-triazol- 3-yl]ethyl]-3,5- bis(trifluoromethyl) benzamide

1.08 510 1 P10 3,5-bis(trifluoromethyl)- N-[1-[2-[5-[(Z)-3,3,3-trifluoroprop-1- enoxy]-2-pyridyl]- 1,2,4-triazol-3-yl]ethyl]benzamide

1.93 540 2 172- 174 P11 N-[1-[2-[5- (difluoromethoxy)- 2-pyridyl]-1,2,4-triazol-3- yl]ethyl]-3,5- bis(trifluoromethyl) benzamide

1.10 496 1 P12 3-(2,2-difluoroethoxy)- N-[1-[2-[5- (difluoromethoxy)pyrimidin-2-yl]-1,2,4- triazol-3-yl]ethyl]-5- (trifluoromethyl)benzamide

0.99 509 1 105- 110

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally, acaricidally and/or fungicidally activeingredients. The mixtures of the compounds of formula I with otherinsecticidally, acaricidally and/or fungicidally active ingredients mayalso have further surprising advantages which can also be described, ina wider sense, as synergistic activity. For example, better tolerance byplants, reduced phytotoxicity, insects can be controlled in theirdifferent development stages or better behaviour during theirproduction, for example during grinding or mixing, during their storageor during their use.

Suitable additions to active ingredients here are, for example,representatives of the following classes of active ingredients:organophosphorus compounds, nitrophenol derivatives, thioureas, juvenilehormones, formamidines, benzophenone derivatives, ureas, pyrrolederivatives, carbamates, pyrethroids, chlorinated hydrocarbons,acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoidsand Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with activeingredients are preferred (where the abbreviation “TX” means “onecompound selected from the compounds defined in the Tables A-1 to A-120and Table P”):

an adjuvant selected from the group of substances consisting ofpetroleum oils (alternative name) (628)+TX,an insect control active substance selected from Abamectin+TX,Acequinocyl+TX, Acetamiprid+TX, Acetoprole+TX, Acrinathrin+TX,Acynonapyr+TX, Afidopyropen+TX, Afoxalaner+TX, Alanycarb+TX,Allethrin+TX, Alpha-Cypermethrin+TX, Alphamethrin+TX, Amidoflumet+TX,Aminocarb+TX, Azocyclotin+TX, Bensultap+TX, Benzoximate+TX,Benzpyrimoxan+TX, Betacyfluthrin+TX, Beta-cypermethrin+TX,Bifenazate+TX, Bifenthrin+TX, Binapacryl+TX, Bioallethrin+TX,Bioallethrin S)-cyclopentylisomer+TX, Bioresmethrin+TX, Bistrifluron+TX,Broflanilide+TX, Brofluthrinate+TX, Bromophos-ethyl+TX, Buprofezine+TX,Butocarboxim+TX, Cadusafos+TX, Carbaryl+TX, Carbosulfan+TX, Cartap+TX,CAS number: 1472050-04-6+TX, CAS number: 1632218-00-8+TX, CAS number:1808115-49-2+TX, CAS number: 2032403-97-5+TX, CAS number:2044701-44-0+TX, CAS number: 2128706-05-6+TX, CAS number:2249718-27-0+TX, Chlorantraniliprole+TX, Chlordane+TX, Chlorfenapyr+TX,Chloroprallethrin+TX, Chromafenozide+TX, Clenpirin+TX, Cloethocarb+TX,Clothianidin+TX, 2-chlorophenyl N-methylcarbamate (CPMC)+TX,Cyanofenphos+TX, Cyantraniliprole+TX, Cyclaniliprole+TX,Cyclobutrifluram+TX, Cycloprothrin+TX, Cycloxaprid+TX, Cycloxaprid+TX,Cyenopyrafen+TX, Cyetpyrafen (or Etpyrafen)+TX, Cyflumetofen+TX,Cyfluthrin+TX, Cyhalodiamide+TX, Cyhalothrin+TX, Cypermethrin+TX,Cyphenothrin+TX, Cyromazine+TX, Deltamethrin+TX, Diafenthiuron+TX,Dialifos+TX, Dibrom+TX, Dicloromezotiaz+TX, Diflovidazine+TX,Diflubenzuron+TX, dimpropyridaz+TX, Dinactin+TX, Dinocap+TX,Dinotefuran+TX, Dioxabenzofos+TX, Emamectin+TX, Empenthrin+TX,Epsilon−momfluorothrin+TX, Epsilon−metofluthrin+TX, Esfenvalerate+TX,Ethion+TX, Ethiprole+TX, Etofenprox+TX, Etoxazole+TX, Famphur+TX,Fenazaquin+TX, Fenfluthrin+TX, Fenitrothion+TX, Fenobucarb+TX,Fenothiocarb+TX, Fenoxycarb+TX, Fenpropathrin+TX, Fenpyroxymate+TX,Fensulfothion+TX, Fenthion+TX, Fentinacetate+TX, Fenvalerate+TX,Fipronil+TX, Flometoquin+TX, Flonicamid+TX, Fluacrypyrim+TX,Fluazaindolizine+TX, Fluazuron+TX, Flubendiamide+TX, Flubenzimine+TX,Flucitrinate+TX, Flucycloxuron+TX, Flucythrinate+TX, Fluensulfone+TX,Flufenerim+TX, Flufenprox+TX, Flufiprole+TX, Fluhexafon+TX,Flumethrin+TX, Fluopyram+TX, Flupentiofenox+TX, Flupyradifurone+TX,Flupyrimin+TX, Fluralaner+TX, Fluvalinate+TX, Fluxametamide+TX,Fosthiazate+TX, Gamma-Cyhalothrin+TX, Gossyplure™+TX, Guadipyr+TX,Halofenozide+TX, Halofenozide+TX, Halofenprox+TX, Heptafluthrin+TX,Hexythiazox+TX, Hydramethylnon+TX, Imicyafos+TX, Imidacloprid+TX,Imiprothrin+TX, Indoxacarb+TX, Iodomethane+TX, Iprodione+TX,Isocycloseram+TX, Isothioate+TX, Ivermectin+TX, Kappa-bifenthrin+TX,Kappa-tefluthrin+TX, Lambda-Cyhalothrin+TX, Lepimectin+TX, Lufenuron+TX,Metaflumizone+TX, Metaldehyde+TX, Metam+TX, Methomyl+TX,Methoxyfenozide+TX, Metofluthrin+TX, Metolcarb+TX, Mexacarbate+TX,Milbemectin+TX, Momfluorothrin+TX, Niclosamide+TX, Nitenpyram+TX,Nithiazine+TX, Omethoate+TX, Oxamyl+TX, Oxazosufyl+TX,Parathion-ethyl+TX, Permethrin+TX, Phenothrin+TX, Phosphocarb+TX,Piperonylbutoxide+TX, Pirimicarb+TX, Pirimiphos-ethyl+TX, Polyhedrosisvirus+TX, Prallethrin+TX, Profenofos+TX, Profenofos+TX, Profluthrin+TX,Propargite+TX, Propetamphos+TX, Propoxur+TX, Prothiophos+TX,Protrifenbute+TX, Pyflubumide+TX, Pymetrozine+TX, Pyraclofos+TX,Pyrafluprole+TX, Pyridaben+TX, Pyridalyl+TX, Pyrifluquinazon+TX,Pyrimidifen+TX, Pyrimostrobin+TX, Pyriprole+TX, Pyriproxyfen+TX,Resmethrin+TX, Sarolaner+TX, Selamectin+TX, Silafluofen+TX,Spinetoram+TX, Spinosad+TX, Spirodiclofen+TX, Spiromesifen+TX,Spiropidion+TX, Spirotetramat+TX, Sulfoxaflor+TX, Tebufenozide+TX,Tebufenpyrad+TX, Tebupirimiphos+TX, Tefluthrin+TX, Temephos+TX,Tetrachloraniliprole+TX, Tetradiphon+TX, Tetramethrin+TX,Tetramethylfluthrin+TX, Tetranactin+TX, Tetraniliprole+TX,Theta-cypermethrin+TX, Thiacloprid+TX, Thiamethoxam+TX, Thiocyclam+TX,Thiodicarb+TX, Thiofanox+TX, Thiometon+TX, Thiosultap+TX, Tioxazafen+TX,Tolfenpyrad+TX, Toxaphene+TX, Tralomethrin+TX, Transfluthrin+TX,Triazamate+TX, Triazophos+TX, Trichlorfon+TX, Trichloronate+TX,Trichlorphon+TX, Triflumezopyrim+TX, Tyclopyrazoflor+TX,Zeta-Cypermethrin+TX, Extract of seaweed and fermentation productderived from melasse+TX, Extract of seaweed and fermentation productderived from melasse comprising urea+TX, amino acids+TX, potassium andmolybdenum and EDTA-chelated manganese+TX, Extract of seaweed andfermented plant products+TX, Extract of seaweed and fermented plantproducts comprising phytohormones+TX, vitamins+TX, EDTA-chelatedcopper+TX, zinc+TX, and iron+TX, Azadirachtin+TX, Bacillus aizawai+TX,Bacillus chitinosporus AQ746 (NRRL Accession No B-21 618)+TX, Bacillusfirmus+TX, Bacillus kurstaki+TX, Bacillus mycoides AQ726 (NRRL AccessionNo. B-21664)+TX, Bacillus pumilus (NRRL Accession No B-30087)+TX,Bacillus pumilus AQ717 (NRRL Accession No. B-21662)+TX, Bacillus sp.AQ178 (ATCC Accession No. 53522)+TX, Bacillus sp. AQ175 (ATCC AccessionNo. 55608)+TX, Bacillus sp. AQ177 (ATCC Accession No. 55609)+TX,Bacillus subtilis unspecified+TX, Bacillus subtilis AQ153 (ATCCAccession No. 55614)+TX, Bacillus subtilis AQ30002 (NRRL Accession No.B-50421)+TX, Bacillus subtilis AQ30004 (NRRL Accession No. B-50455)+TX,Bacillus subtilis AQ713 (NRRL Accession No. B-21661)+TX, Bacillussubtilis AQ743 (NRRL Accession No. B-21665)+TX, Bacillus thuringiensisAQ52 (NRRL Accession No. B-21619)+TX, Bacillus thuringiensis BD#32 (NRRLAccession No B-21530)+TX, Bacillus thuringiensis subspec. kurstaki BMP123+TX, Beauveria bassiana+TX, D-limonene+TX, Granulovirus+TX,Harpin+TX, Helicoverpa armigera Nucleopolyhedrovirus+TX, Helicoverpa zeaNucleopolyhedrovirus+TX, Heliothis virescens Nucleopolyhedrovirus+TX,Heliothis punctigera Nucleopolyhedrovirus+TX, Metarhizium spp.+TX,Muscodor albus 620 (NRRL Accession No. 30547)+TX, Muscodor roseus A3-5(NRRL Accession No. 30548)+TX, Neem tree based products+TX, Paecilomycesfumosoroseus+TX, Paecilomyces lilacinus+TX, Pasteuria nishizawae+TX,Pasteuria penetrans+TX, Pasteuria ramosa+TX, Pasteuria thornei+TX,Pasteuria usgae+TX, P-cymene+TX, Plutella xylostella Granulosisvirus+TX, Plutella xylostella Nucleopolyhedrovirus+TX, Polyhedrosisvirus+TX, pyrethrum+TX, QRD 420 (a terpenoid blend)+TX, QRD 452 (aterpenoid blend)+TX, QRD 460 (a terpenoid blend)+TX, Quillajasaponaria+TX, Rhodococcus globerulus AQ719 (NRRL Accession NoB-21663)+TX, Spodoptera frugiperda Nucleopolyhedrovirus+TX, Streptomycesgalbus (NRRL Accession No. 30232)+TX, Streptomyces sp. (NRRL AccessionNo. B-30145)+TX, Terpenoid blend+TX, and Verticillium spp.,an algicide selected from the group of substances consisting ofbethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, coppersulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen(232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX,nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine(730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX,an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, Cyclobutrifluram+TX, doramectin(alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate(291)+TX, eprinomectin (alternative name) [CCN]+TX, ivermectin(alternative name) [CCN]+TX, milbemycin oxime (alternative name)[CCN]+TX, moxidectin (alternative name) [CCN]+TX, piperazine [CCN]+TX,selamectin (alternative name) [CCN]+TX, spinosad (737) and thiophanate(1435)+TX,an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, a bactericideselected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin(483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickelbis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin(580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline(611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole(658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX,tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,a biological agent selected from the group of substances consisting ofAdoxophyes orana GV (alternative name) (12)+TX, Agrobacteriumradiobacter (alternative name) (13)+TX, Amblyseius spp. (alternativename) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX,Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis(alternative name) (33)+TX, Aphidius colemani (alternative name)(34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographacalifornica NPV (alternative name) (38)+TX, Bacillus firmus (alternativename) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX,Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillusthuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillusthuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillusthuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveriabassiana (alternative name) (53)+TX, Beauveria brongniartii (alternativename) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX,Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonellaGV (alternative name) (191)+TX, Dacnusa sibirica (alternative name)(212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa(scientific name) (293)+TX, Eretmocerus eremicus (alternative name)(300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX,Heterorhabditis bacteriophora and H. megidis (alternative name)(433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastixdactylopii (alternative name) (488)+TX, Macrolophus caliginosus(alternative name) (491)+TX, Mamestra brassicae NPV (alternative name)(494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhiziumanisopliae var. acridum (scientific name) (523)+TX, Metarhiziumanisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp.(alternative name) (596)+TX, Paecilomyces fumosoroseus (alternativename) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX,Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientificname) (741)+TX, Steinernema bibionis (alternative name) (742)+TX,Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae(alternative name) (742)+TX, Steinernema glaseri (alternative name)(742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernemariobravis (alternative name) (742)+TX, Steinernema scapterisci(alternative name) (742)+TX, Steinernema spp. (alternative name)(742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromusoccidentalis (alternative name) (844) and Verticillium lecanii(alternative name) (848)+TX,a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan(alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif(alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX,thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name)[CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternativename) [CCN]+TX, an insect pheromone selected from the group ofsubstances consisting of (E)-dec-5-en-1-yl acetate with(E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tridec-4-en-1-yl acetate(IUPAC name) (829)+TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin(alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX,codlelure (alternative name) [CCN]+TX, codlemone (alternative name)(167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX,dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate(IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name)(284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name)[CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternativename) (420)+TX, grandlure (421)+TX, grandlure I (alternative name)(421)+TX, grandlure II (alternative name) (421)+TX, grandlure III(alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX,hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol(alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX,lineatin (alternative name) [CCN]+TX, litlure (alternative name)[CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX,megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternativename) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate(IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name)(589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternativename) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX,sordidin (alternative name) (736)+TX, sulcatol (alternative name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure(839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁(alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX,trimedlure C (alternative name) (839) and trunc-call (alternative name)[CCN]+TX,an insect repellent selected from the group of substances consisting of2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX,butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name)(1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name)(1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX,a molluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole[394730-71-3]+TX,a nematicide selected from the group of substances consisting ofAKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/ChemicalAbstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstractsname) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPACname) (1063)+TX, 1,3-dichloropropene (233)+TX,3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstractsname) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name)(980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPACname) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX,abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz[CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX,carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX,cloethocarb (999)+TX, Cyclobutrifluram+TX, cytokinins (alternative name)(210)+TX, dazomet (216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos(1044)+TX, dichlofenthion (1051)+TX, dicliphos (alternative name)+TX,dimethoate (262)+TX, doramectin (alternative name) [CCN]+TX, emamectin(291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name)[CCN]+TX, ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos(326)+TX, fenpyrad (alternative name)+TX, fensulfothion (1158)+TX,fosthiazate (408)+TX, fosthietan (1196)+TX, furfural (alternative name)[CCN]+TX, GY-81 (development code) (423)+TX, heterophos [CCN]+TX,iodomethane (IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos(1231)+TX, ivermectin (alternative name) [CCN]+TX, kinetin (alternativename) (210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium(alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternativename) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrotheciumverrucaria composition (alternative name) (565)+TX, NC-184 (compoundcode)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX,phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin(alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternativename)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/ChemicalAbstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name)(210)+TX, fluensulfone [318290-98-1]+TX, fluopyram+TX,a nitrification inhibitor selected from the group of substancesconsisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (alternative name) (720)+TX,a rodenticide selected from the group of substances consisting of2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX,coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX,crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX,diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX,fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadinehydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogencyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX,magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX,norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name)(640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite[CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite[CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX,strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zincphosphide (640)+TX,a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (alternative name) (324)+TX, MB-599 (developmentcode) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide(649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (developmentcode) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide(1406)+TX,an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX,a virucide selected from the group of substances consisting of imanin(alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,a wound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX,a biologically active substance selected from1,1-bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenylbenzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX,4-chlorophenyl phenyl sulfone+TX, acetoprole+TX, aldoxycarb+TX,amidithion+TX, amidothioate+TX, amiton+TX, amiton hydrogen oxalate+TX,amitraz+TX, aramite+TX, arsenous oxide+TX, azobenzene+TX, azothoate+TX,benomyl+TX, benoxafos+TX, benzyl benzoate+TX, bixafen+TX,brofenvalerate+TX, bromocyclen+TX, bromophos+TX, bromopropylate+TX,buprofezin+TX, butocarboxim+TX, butoxycarboxim+TX, butylpyridaben+TX,calcium polysulfide+TX, camphechlor+TX, carbanolate+TX,carbophenothion+TX, cymiazole+TX, chinomethionat+TX, chlorbenside+TX,chlordimeform+TX, chlordimeform hydrochloride+TX, chlorfenethol+TX,chlorfenson+TX, chlorfensulfide+TX, chlorobenzilate+TX,chloromebuform+TX, chloromethiuron+TX, chloropropylate+TX,chlorthiophos+TX, cinerin I+TX, cinerin II+TX, cinerins+TX,closantel+TX, coumaphos+TX, crotamiton+TX, crotoxyphos+TX, cufraneb+TX,cyanthoate+TX, DCPM+TX, DDT+TX, demephion+TX, demephion-O+TX,demephion-S+TX, demeton-methyl+TX, demeton-O+TX, demeton-O-methyl+TX,demeton-S+TX, demeton-S-methyl+TX, demeton-S-methylsulfon+TX,dichlofluanid+TX, dichlorvos+TX, dicliphos+TX, dienochlor+TX,dimefox+TX, dinex+TX, dinex-diclexine+TX, dinocap-4+TX, dinocap-6+TX,dinocton+TX, dinopenton+TX, dinosulfon+TX, dinoterbon+TX, dioxathion+TX,diphenyl sulfone+TX, disulfiram+TX, DNOC+TX, dofenapyn+TX,doramectin+TX, endothion+TX, eprinomectin+TX, ethoate-methyl+TX,etrimfos+TX, fenazaflor+TX, fenbutatin oxide+TX, fenothiocarb+TX,fenpyrad+TX, fen-pyroximate+TX, fenpyrazamine+TX, fenson+TX,fentrifanil+TX, flubenzimine+TX, flucycloxuron+TX, fluenetil+TX,fluorbenside+TX, FMC 1137+TX, formetanate+TX, formetanatehydrochloride+TX, formparanate+TX, gamma-HCH+TX, glyodin+TX,halfenprox+TX, hexadecyl cyclopropanecarboxylate+TX, isocarbophos+TX,jasmolin I+TX, jasmolin II+TX, jodfenphos+TX, lindane+TX, malonoben+TX,mecarbam+TX, mephosfolan+TX, mesulfen+TX, methacrifos+TX, methylbromide+TX, metolcarb+TX, mexacarbate+TX, milbemycin oxime+TX,mipafox+TX, monocrotophos+TX, morphothion+TX, moxidectin+TX, naled+TX,4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one+TX,nifluridide+TX, nikkomycins+TX, nitrilacarb+TX, nitrilacarb 1:1 zincchloride complex+TX, omethoate+TX, oxydeprofos+TX, oxydisulfoton+TX,pp′-DDT+TX, parathion+TX, permethrin+TX, phenkapton+TX, phosalone+TX,phosfolan+TX, phosphamidon+TX, polychloroterpenes+TX, polynactins+TX,proclonol+TX, promacyl+TX, propoxur+TX, prothidathion+TX, prothoate+TX,pyrethrin I+TX, pyrethrin II+TX, pyrethrins+TX, pyridaphenthion+TX,pyrimitate+TX, quinalphos+TX, quintiofos+TX, R-1492+TX, phosglycin+TX,rotenone+TX, schradan+TX, sebufos+TX, selamectin+TX, sophamide+TX,SSI-121+TX, sulfiram+TX, sulfluramid+TX, sulfotep+TX, sulfur+TX,diflovidazin+TX, tau-fluvalinate+TX, TEPP+TX, terbam+TX, tetradifon+TX,tetrasul+TX, thiafenox+TX, thiocarboxime+TX, thiofanox+TX, thiometon+TX,thioquinox+TX, thuringiensin+TX, triamiphos+TX, triarathene+TX,triazophos+TX, triazuron+TX, trifenofos+TX, trinactin+TX,vamidothion+TX, vaniliprole+TX, bethoxazin+TX, copper dioctanoate+TX,copper sulfate+TX, cybutryne+TX, dichlone+TX, dichlorophen+TX,endothal+TX, fentin+TX, hydrated lime+TX, nabam+TX, quinoclamine+TX,quinonamid+TX, simazine+TX, triphenyltin acetate+TX, triphenyltinhydroxide+TX, crufomate+TX, piperazine+TX, thiophanate+TX,chloralose+TX, fenthion+TX, pyridin-4-amine+TX, strychnine+TX,1-hydroxy-1H-pyridine-2-thione+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide+TX, 8-hydroxyquinolinesulfate+TX, bronopol+TX, copper hydroxide+TX, cresol+TX,dipyrithione+TX, dodicin+TX, fenaminosulf+TX, formaldehyde+TX,hydrargaphen+TX, kasugamycin+TX, kasugamycin hydrochloride hydrate+TX,nickel bis(dimethyldithiocarbamate)+TX, nitrapyrin+TX, octhilinone+TX,oxolinic acid+TX, oxytetracycline+TX, potassium hydroxyquinolinesulfate+TX, probenazole+TX, streptomycin+TX, streptomycinsesquisulfate+TX, tecloftalam+TX, thiomersal+TX, Adoxophyes orana GV+TX,Agrobacterium radiobacter+TX, Amblyseius spp.+TX, Anagrapha falciferaNPV+TX, Anagrus atomus+TX, Aphelinus abdominalis+TX, Aphidiuscolemani+TX, Aphidoletes aphidimyza+TX, Autographa californica NPV+TX,Bacillus sphaericus Neide+TX, Beauveria brongniartii+TX, Chrysoperlacarnea+TX, Cryptolaemus montrouzieri+TX, Cydia pomonella GV+TX, Dacnusasibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmoceruseremicus+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamiaconvergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX,Mamestra brassicae NPV+TX, Metaphycus helvolus+TX, Metarhiziumanisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX,Neodiprion sertifer NPV and N. lecontei NPV+TX, Orius spp.+TX,Paecilomyces fumosoroseus+TX, Phytoseiulus persimilis+TX, Steinernemabibionis+TX, Steinernema carpocapsae+TX, Steinernema feltiae+TX,Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernemariobravis+TX, Steinernema scapterisci+TX, Steinernema spp.+TX,Trichogramma spp.+TX, Typhlodromus occidentalis+TX, Verticilliumlecanii+TX, apholate+TX, bisazir+TX, busulfan+TX, dimatif+TX, hemel+TX,hempa+TX, metepa+TX, methiotepa+TX, methyl apholate+TX, morzid+TX,penfluron+TX, tepa+TX, thiohempa+TX, thiotepa+TX, tretamine+TX,uredepa+TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol+TX,(E)-tridec-4-en-1-yl acetate+TX, (E)-6-methylhept-2-en-4-ol+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate+TX, (Z)-dodec-7-en-1-ylacetate+TX, (Z)-hexadec-11-enal+TX, (Z)-hexadec-11-en-1-yl acetate+TX,(Z)-hexadec-13-en-11-yn-1-yl acetate+TX, (Z)-icos-13-en-10-one+TX,(Z)-tetradec-7-en-1-al+TX, (Z)-tetradec-9-en-1-ol+TX,(Z)-tetradec-9-en-1-yl acetate+TX, (7E,9Z)-dodeca-7,9-dien-1-ylacetate+TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate+TX, 14-methyloctadec-1-ene+TX,4-methylnonan-5-ol with 4-methylnonan-5-one+TX, alpha-multistriatin+TX,brevicomin+TX, codlelure+TX, codlemone+TX, cuelure+TX, disparlure+TX,dodec-8-en-1-yl acetate+TX, dodec-9-en-1-yl acetate+TX, dodeca-8+TX,10-dien-1-yl acetate+TX, dominicalure+TX, ethyl 4-methyloctanoate+TX,eugenol+TX, frontalin+TX, grandlure+TX, grandlure I+TX, grandlure II+TX,grandlure III+TX, grandlure IV+TX, hexalure+TX, ipsdienol+TX,ipsenol+TX, japonilure+TX, lineatin+TX, litlure+TX, looplure+TX,medlure+TX, megatomoic acid+TX, methyl eugenol+TX, muscalure+TX,octadeca-2,13-dien-1-yl acetate+TX, octadeca-3,13-dien-1-yl acetate+TX,orfralure+TX, oryctalure+TX, ostramone+TX, siglure+TX, sordidin+TX,sulcatol+TX, tetradec-11-en-1-yl acetate+TX, trimedlure+TX, trimedlureA+TX, trimedlure B₁+TX, trimedlure B₂+TX, trimedlure C+TX,trunc-call+TX, 2-(octylthio)ethanol+TX, butopyronoxyl+TX,butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutylphthalate+TX, dibutyl succinate+TX, diethyltoluamide+TX, dimethylcarbate+TX, dimethyl phthalate+TX, ethyl hexanediol+TX, hexamide+TX,methoquin-butyl+TX, methylneodecanamide+TX, oxamate+TX, picaridin+TX,1-dichloro-1-nitroethane+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane+TX, 1,2-dichloropropane with1,3-dichloropropene+TX, 1-bromo-2-chloroethane+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate+TX,2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate+TX,2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate+TX,2-(2-butoxyethoxy)ethyl thiocyanate+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate+TX,2-(4-chloro-3,5-xylyloxy)ethanol+TX, 2-chlorovinyl diethyl phosphate+TX,2-imidazolidone+TX, 2-isovalerylindan-1,3-dione+TX,2-methyl(prop-2-ynyl)aminophenyl methylcarbamate+TX, 2-thiocyanatoethyllaurate+TX, 3-bromo-1-chloroprop-1-ene+TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate+TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate+TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate+TX, acethion+TX, acrylonitrile+TX, aldrin+TX,allosamidin+TX, allyxycarb+TX, alpha-ecdysone+TX, aluminiumphosphide+TX, aminocarb+TX, anabasine+TX, athidathion+TX,azamethiphos+TX, Bacillus thuringiensis delta endotoxins+TX, bariumhexafluorosilicate+TX, barium polysulfide+TX, barthrin+TX, Bayer22/190+TX, Bayer 22408+TX, beta-cyfluthrin+TX, beta-cypermethrin+TX,bioethanomethrin+TX, biopermethrin+TX, bis(2-chloroethyl) ether+TX,borax+TX, bromfenvinfos+TX, bromo-DDT+TX, bufencarb+TX, butacarb+TX,butathiofos+TX, butonate+TX, calcium arsenate+TX, calcium cyanide+TX,carbon disulfide+TX, carbon tetrachloride+TX, cartap hydrochloride+TX,cevadine+TX, chlorbicyclen+TX, chlordane+TX, chlordecone+TX,chloroform+TX, chloropicrin+TX, chlorphoxim+TX, chlorprazophos+TX,cis-resmethrin+TX, cismethrin+TX, clocythrin+TX, copperacetoarsenite+TX, copper arsenate+TX, copper oleate+TX, coumithoate+TX,cryolite+TX, CS 708+TX, cyanofenphos+TX, cyanophos+TX, cyclethrin+TX,cythioate+TX, d-tetramethrin+TX, DAEP+TX, dazomet+TX, decarbofuran+TX,diamidafos+TX, dicapthon+TX, dichlofenthion+TX, dicresyl+TX,dicyclanil+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX,dilor+TX, dimefluthrin+TX, dimetan+TX, dimethrin+TX, dimethylvinphos+TX,dimetilan+TX, dinoprop+TX, dinosam+TX, dinoseb+TX, diofenolan+TX,dioxabenzofos+TX, dithicrofos+TX, DSP+TX, ecdysterone+TX, El 1642+TX,EMPC+TX, EPBP+TX, etaphos+TX, ethiofencarb+TX, ethyl formate+TX,ethylene dibromide+TX, ethylene dichloride+TX, ethylene oxide+TX,EXD+TX, fenchlorphos+TX, fenethacarb+TX, fenitrothion+TX, fenoxacrim+TX,fenpirithrin+TX, fensulfothion+TX, fenthion-ethyl+TX, flucofuron+TX,fosmethilan+TX, fospirate+TX, fosthietan+TX, furathiocarb+TX,furethrin+TX, guazatine+TX, guazatine acetates+TX, sodiumtetrathiocarbonate+TX, halfenprox+TX, HCH+TX, HEOD+TX, heptachlor+TX,heterophos+TX, HHDN+TX, hydrogen cyanide+TX, hyquincarb+TX, IPSP+TX,isazofos+TX, isobenzan+TX, isodrin+TX, isofenphos+TX, isolane+TX,isoprothiolane+TX, isoxathion+TX, juvenile hormone I+TX, juvenilehormone II+TX, juvenile hormone III+TX, kelevan+TX, kinoprene+TX, leadarsenate+TX, leptophos+TX, lirimfos+TX, lythidathion+TX, m-cumenylmethylcarbamate+TX, magnesium phosphide+TX, mazidox+TX, mecarphon+TX,menazon+TX, mercurous chloride+TX, mesulfenfos+TX, metam+TX,metam-potassium+TX, metam-sodium+TX, methanesulfonyl fluoride+TX,methocrotophos+TX, methoprene+TX, methothrin+TX, methoxychlor+TX, methylisothiocyanate+TX, methylchloroform+TX, methylene chloride+TX,metoxadiazone+TX, mirex+TX, naftalofos+TX, naphthalene+TX, NC-170+TX,nicotine+TX, nicotine sulfate+TX, nithiazine+TX, nornicotine+TX,O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate+TX, O,O-diethylO-6-methyl-2-propylpyrimidin-4-yl phosphorothioate+TX,O,O,O′,O′-tetrapropyl dithiopyrophosphate+TX, oleic acid+TX,para-dichlorobenzene+TX, parathion-methyl+TX, pentachlorophenol+TX,pentachlorophenyl laurate+TX, PH 60-38+TX, phenkapton+TX,phosnichlor+TX, phosphine+TX, phoxim-methyl+TX, pirimetaphos+TX,polychlorodicyclopentadiene isomers+TX, potassium arsenite+TX, potassiumthiocyanate+TX, precocene I+TX, precocene II+TX, precocene III+TX,primidophos+TX, profluthrin+TX, promecarb+TX, prothiofos+TX,pyrazophos+TX, pyresmethrin+TX, quassia+TX, quinalphos-methyl+TX,quinothion+TX, rafoxanide+TX, resmethrin+TX, rotenone+TX, kadethrin+TX,ryania+TX, ryanodine+TX, sabadilla)+TX, schradan+TX, sebufos+TX,SI-0009+TX, thiapronil+TX, sodium arsenite+TX, sodium cyanide+TX, sodiumfluoride+TX, sodium hexafluorosilicate+TX, sodiumpentachlorophenoxide+TX, sodium selenate+TX, sodium thiocyanate+TX,sulcofuron+TX, sulcofuron-sodium+TX, sulfuryl fluoride+TX, sulprofos+TX,tar oils+TX, tazimcarb+TX, TDE+TX, tebupirimfos+TX, temephos+TX,terallethrin+TX, tetrachloroethane+TX, thicrofos+TX, thiocyclam+TX,thiocyclam hydrogen oxalate+TX, thionazin+TX, thiosultap+TX,thiosultap-sodium+TX, tralomethrin+TX, transpermethrin+TX,triazamate+TX, trichlormetaphos-3+TX, trichloronat+TX, trimethacarb+TX,tolprocarb+TX, triclopyricarb+TX, triprene+TX, veratridine+TX,veratrine+TX, XMC+TX, zetamethrin+TX, zinc phosphide+TX, zolaprofos+TX,and meperfluthrin+TX, tetramethylfluthrin+TX, bis(tributyltin) oxide+TX,bromoacetamide+TX, ferric phosphate+TX, niclosamide-olamine+TX,tributyltin oxide+TX, pyrimorph+TX, trifenmorph+TX,1,2-dibromo-3-chloropropane+TX, 1,3-dichloropropene+TX,3,4-dichlorotetrahydrothiophene 1,1-dioxide+TX,3-(4-chlorophenyl)-5-methylrhodanine+TX,5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid+TX,6-isopentenylaminopurine+TX, benclothiaz+TX, cytokinins+TX, DCIP+TX,furfural+TX, isamidofos+TX, kinetin+TX, Myrothecium verrucariacomposition+TX, tetrachlorothiophene+TX, xylenols+TX, zeatin+TX,potassium ethylxanthate+TX, acibenzolar+TX, acibenzolar-S-methyl+TX,Reynoutria sachalinensis extract+TX, alpha-chlorohydrin+TX, antu+TX,barium carbonate+TX, bisthiosemi+TX, brodifacoum+TX, bromadiolone+TX,bromethalin+TX, chlorophacinone+TX, cholecalciferol+TX, coumachlor+TX,coumafuryl+TX, coumatetralyl+TX, crimidine+TX, difenacoum+TX,difethialone+TX, diphacinone+TX, ergocalciferol+TX, flocoumafen+TX,fluoroacetamide+TX, flupropadine+TX, flupropadine hydrochloride+TX,norbormide+TX, phosacetim+TX, phosphorus+TX, pindone+TX, pyrinuron+TX,scilliroside+TX, sodium fluoroacetate+TX, thallium sulfate+TX,warfarin+TX, 2-(2-butoxyethoxy)ethyl piperonylate+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone+TX, farnesol withnerolidol+TX, verbutin+TX, MGK 264+TX, piperonyl butoxide+TX,piprotal+TX, propyl isomer+TX, S421+TX, sesamex+TX, sesasmolin+TX,sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copperoxychloride+TX, dicyclopentadiene+TX, thiram+TX, zinc naphthenate+TX,ziram+TX, imanin+TX, ribavirin+TX, mercuric oxide+TX,thiophanate-methyl+TX, azaconazole+TX, bitertanol+TX, bromuconazole+TX,cyproconazole+TX, difenoconazole+TX, diniconazole+TX, epoxiconazole+TX,fenbuconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX,furametpyr+TX, hexaconazole+TX, imazalil+TX, imibenconazole+TX,ipconazole+TX, metconazole+TX, myclobutanil+TX, paclobutrazole+TX,pefurazoate+TX, penconazole+TX, prothioconazole+TX, pyrifenox+TX,prochloraz+TX, propiconazole+TX, pyrisoxazole+TX, simeconazole+TX,tebuconazole+TX, tetraconazole+TX, triadimefon+TX, triadimenol+TX,triflumizole+TX, triticonazole+TX, ancymidol+TX, fenarimol+TX,nuarimol+TX, bupirimate+TX, dimethirimol+TX, ethirimol+TX, dodemorph+TX,fenpropidine+TX, fenpropimorph+TX, spiroxamine+TX, tridemorph+TX,cyprodinil+TX, mepanipyrim+TX, pyrimethanil+TX, fenpiclonil+TX,fludioxonil+TX, benalaxyl+TX, furalaxyl+TX, metalaxyl+TX,R-metalaxyl+TX, ofurace+TX, oxadixyl+TX, carbendazim+TX, debacarb+TX,fuberidazole+TX, thiabendazole+TX, chlozolinate+TX, dichlozoline+TX,myclozoline+TX, procymidone+TX, vinclozoline+TX, boscalid+TX,carboxin+TX, fenfuram+TX, flutolanil+TX, mepronil+TX, oxycarboxin+TX,penthiopyrad+TX, thifluzamide+TX, dodine+TX, iminoctadine+TX,azoxystrobin+TX, dimoxystrobin+TX, enestroburin+TX, fenaminstrobin+TX,flufenoxystrobin+TX, fluoxastrobin+TX, kresoxim-methyl+TX,metominostrobin+TX, trifloxystrobin+TX, orysastrobin+TX,picoxystrobin+TX, pyraclostrobin+TX, pyrametostrobin+TX,pyraoxystrobin+TX, ferbam+TX, mancozeb+TX, maneb+TX, metiram+TX,propineb+TX, zineb+TX, captafol+TX, captan+TX, fluoroimide+TX,folpet+TX, tolylfluanid+TX, bordeaux mixture+TX, copper oxide+TX,mancopper+TX, oxine-copper+TX, nitrothal-isopropyl+TX, edifenphos+TX,iprobenphos+TX, phosdiphen+TX, tolclofos-methyl+TX, anilazine+TX,benthiavalicarb+TX, blasticidin-S+TX, chloroneb+TX, chlorothalonil+TX,cyflufenamid+TX, cymoxanil+TX, Cyclobutrifluram+TX, diclocymet+TX,diclomezine+TX, dicloran+TX, diethofencarb+TX, dimethomorph+TX,flumorph+TX, dithianon+TX, ethaboxam+TX, etridiazole+TX, famoxadone+TX,fenamidone+TX, fenoxanil+TX, ferimzone+TX, fluazinam+TX,flubeneteram+TX; fluopicolide+TX, flusulfamide+TX, fluxapyroxad+TX,fenhexamid+TX, fosetyl-aluminium+TX, hymexazol+TX, iprovalicarb+TX,cyazofamid+TX, methasulfocarb+TX, metrafenone+TX, pencycuron+TX,phthalide+TX, polyoxins+TX, propamocarb+TX, pyribencarb+TX,proquinazid+TX, pyroquilon+TX, pyriofenone+TX, quinoxyfen+TX,quintozene+TX, tiadinil+TX, triazoxide+TX, tricyclazole+TX,triforine+TX, validamycin+TX, valifenalate+TX, zoxamide+TX,mandipropamid+TX, isopyrazam+TX, sedaxane+TX, benzovindiflupyr+TX,pydiflumetofen+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid (3′,4′,5′-trifluoro-biphenyl-2-yl)-amide+TX, isoflucypram+TX,isotianil+TX, dipymetitrone+TX,6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile+TX,2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX,4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile+TX,(R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX,4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine+TX,4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine+TX,fluindapyr+TX, coumethoxystrobin (jiaxiangjunzhi)+TX, Ivbenmixianan+TX,dichlobentiazox+TX, mandestrobin+TX,3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone+TX,2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol+TX,oxathiapiprolin+TX, tert-butylN-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate+TX,pyraziflumid+TX, inpyrfluxam+TX, trolprocarb+TX, mefentrifluconazole+TX,ipfentrifluconazole+TX,2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX,N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX,N′-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine+TX,[2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate+TX, but-3-ynylN-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate+TX,methylN-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate+TX,3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine+TX,pyridachlometyl+TX,3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX,1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one+TX,1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one+TX,aminopyrifen+TX, ametoctradin+TX, amisulbrom+TX, penflufen+TX,(Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX,florylpicoxamid+TX, fenpicoxamid+TX, tebufloquin+TX, ipflufenoquin+TX,quinofumelin+TX, isofetamid+TX,N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX,N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX,benzothiostrobin+TX, phenamacril+TX, 5-amino-1,3,4-thiadiazole-2-thiolzinc salt (2:1)+TX, fluopyram+TX, flutianil+TX, fluopimomide+TX,pyrapropoyne+TX, picarbutrazox+TX,2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide+TX,2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide+TX,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX,metyltetraprole+TX,2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-1-yl)pyridine-3-carboxamide+TX,α-(1,1-dimethylethyl)-α-[4′-(trifluoromethoxy)[1,1′-biphenyl]-4-yl]-5-pyrimidinemethanol+TX,fluoxapiprolin+TX, enoxastrobin+TX,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX,trinexapac+TX, coumoxystrobin+TX, zhongshengmycin+TX, thiodiazolecopper+TX, zinc thiazole+TX, amectotractin+TX, iprodione+TX, mixtures of(N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide+TX,N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX,N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX,1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX,1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX,3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX,N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX,4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX,5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX,ethyl1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate+TX,andN,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX),wherein the compound in the mixture, other than TX, may be prepared fromthe methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348and WO 2017/118689,2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX(this compound may be prepared from the methods described in WO2017/029179),2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX(this compound may be prepared from the methods described in WO2017/029179),3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX(this compound may be prepared from the methods described in WO2016/156290),3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX(this compound may be prepared from the methods described in WO2016/156290), (4-phenoxyphenyl)methyl2-amino-6-methyl-pyridine-3-carboxylate+TX (this compound may beprepared from the methods described in WO 2014/006945),2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone+TX(this compound may be prepared from the methods described in WO2011/138281),N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide+TX,N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX,(Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX(this compound may be prepared from the methods described in WO2018/153707),N′-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX,N′-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine+TX(this compound may be prepared from the methods described in WO2016/202742), and2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX(this compound may be prepared from the methods described in WO2014/095675),microbials including: Acinetobacter twoffii+TX, Acremoniumalternatum+TX+TX, Acremonium cephalosporium+TX+TX, Acremoniumdiospyri+TX, Acremonium obclavatum+TX, Adoxophyes orana granulovirus(AdoxGV) (Capex®)+TX, Agrobacterium radiobacter strain K84(Galltrol-A®)+TX, Alternaria alternate+TX, Alternaria cassia+TX,Alternaria destruens (Smolder®)+TX, Ampelomyces quisqualis (AQ10@)+TX,Aspergillus flavus AF36 (AF36@)+TX, Aspergillus flavus NRRL 21882(Aflaguard®)+TX, Aspergillus spp.+TX, Aureobasidium pullulans+TX,Azospirillum+TX, (MicroAZ®+TX, TAZO B®)+TX, Azotobacter+TX, Azotobacterchroocuccum (Azotomeal®)+TX, Azotobacter cysts (Bionatural BloomingBlossoms®)+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX,Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strainAQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX,Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX,Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX,VOTiVO®)+TX, Bacillus firmus strain 1-1582+TX, Bacillus macerans+TX,Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoidesstrain AQ726+TX, Bacillus papillae (Milky Spore Powder®)+TX, Bacilluspumilus spp.+TX, Bacillus pumilus strain GB34 (Yield Shield®)+TX,Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808(Sonata®+TX, Ballad Plus®)+TX, Bacillus spahericus (VectoLex®)+TX,Bacillus spp.+TX, Bacillus spp. strain AQ175+TX, Bacillus spp. strainAQ177+TX, Bacillus spp. strain AQ178+TX, Bacillus subtilis strain QST713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strainQST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilisstrain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilisstrain QST3004+TX, Bacillus subtilis var. amyloliquefaciens strain FZB24(Taegro®+TX, Rhizopro®)+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillusthuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91(Agree®)+TX, Bacillus thuringiensis israelensis (BMP123®+TX,Aquabac®+TX, VectoBac®)+TX, Bacillus thuringiensis kurstaki(Javelin®+TX, Deliver®+TX, CryMax®+TX, Bonide®+TX, Scutella WP®+TX,Turilav WP®+TX, Astuto®+TX, Dipel WP®+TX, Biobit®+TX, Foray®)+TX,Bacillus thuringiensis kurstaki BMP 123 (Baritone®)+TX, Bacillusthuringiensis kurstaki HD-1 (Bioprotec-CAF/3P®)+TX, Bacillusthuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX,Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, bacteriaspp. (GROWMEND®+TX, GROWSWEET®+TX, Shootup®)+TX, bacteriophage ofClavipacter michiganensis (AgriPhage®)+TX, Bakflor®+TX, Beauveriabassiana (Beaugenic®+TX, Brocaril WP®)+TX, Beauveria bassiana GHA(Mycotrol ES®+TX, Mycotrol O®+TX, BotaniGuard®)+TX, Beauveriabrongniartii (Engerlingspilz®+TX, Schweizer Beauveria®+TX,Melocont®)+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobiumjaponicum (TerraMax®)+TX, Brevibacillus brevis+TX, Bacillusthuringiensis tenebrionis (Novodor®)+TX, BtBooster+TX, Burkholderiacepacia (Deny®+TX, Intercept®+TX, Blue Circle®)+TX, Burkholderiagladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadianthistle fungus (CBH Canadian Bioherbicide®)+TX, Candida butyri+TX,Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candidaguilliermondii+TX, Candida melibiosica+TX, Candida oleophila strainO+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candidapulcherrima+TX, Candida reukaufii+TX, Candida saitoana (Bio-Coat®+TX,Biocure®)+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX,Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes(Nova-Cide®)+TX, Chaetomium globosum (Nova-Cide®)+TX, Chromobacteriumsubtsugae strain PRAA4-1T (Grandevo®)+TX, Cladosporiumcladosporioides+TX, Cladosporium oxysporum+TX, Cladosporiumchlorocephalum+TX, Cladosporium spp.+TX, Cladosporium tenuissimum+TX,Clonostachys rosea (EndoFine®)+TX, Colletotrichum acutatum+TX,Coniothyrium minitans (Cotans WG®)+TX, Coniothyrium spp.+TX,Cryptococcus albidus (YIELDPLUS®)+TX, Cryptococcus humicola+TX,Cryptococcus infirmo-miniatus+TX, Cryptococcus laurentii+TX,Cryptophlebia leucotreta granulovirus (Cryptex®)+TX, Cupriaviduscampinensis+TX, Cydia pomonella granulovirus (CYD-X®)+TX, Cydiapomonella granulovirus (Madex®+TX, Madex Plus®+TX, MadexMax/Carpovirusine®)+TX, Cylindrobasidium laeve (Stumpout®)+TX,Cylindrocladium+TX, Debaryomyces hansenii+TX, Drechslerahawaiinensis+TX, Enterobacter cloacae+TX, Enterobacteriaceae+TX,Entomophtora virulenta (Vektor®)+TX, Epicoccum nigrum+TX, Epicoccumpurpurascens+TX, Epicoccum spp.+TX, Filobasidium floriforme+TX, Fusariumacuminatum+TX, Fusarium chlamydosporum+TX, Fusarium oxysporum(Fusaclean®/Biofox C®)+TX, Fusarium proliferatum+TX, Fusarium spp.+TX,Galactomyces geotrichum+TX, Gliocladium catenulatum (Primastop®+TX,Prestop®)+TX, Gliocladium roseum+TX, Gliocladium spp. (SoilGard®)+TX,Gliocladium virens (Soilgard®)+TX, Granulovirus (Granupom®)+TX,Halobacillus halophilus+TX, Halobacillus litoralis+TX, Halobacillustrueperi+TX, Halomonas spp.+TX, Halomonas subglaciescola+TX, Halovibriovariabilis+TX, Hanseniaspora uvarum+TX, Helicoverpa armigeranucleopolyhedrovirus (Helicovex®)+TX, Helicoverpa zea nuclearpolyhedrosis virus (Gemstar®)+TX, Isoflavone—formononetin(Myconate®)+TX, Kloeckera apiculata+TX, Kloeckera spp.+TX, Lagenidiumgiganteum (Laginex®)+TX, Lecanicillium longisporum (Vertiblast®)+TX,Lecanicillium muscarium (Vertikil®)+TX, Lymantria Disparnucleopolyhedrosis virus (Disparvirus®)+TX, Marinococcus halophilusTX,Meira geulakonigii+TX, Metarhizium anisopliae (Met52®)+TX, Metarhiziumanisopliae (Destruxin WP®)+TX, Metschnikowia fruticola (Shemer®)+TX,Metschnikowia pulcherrima+TX, Microdochium dimerum (Antibot®)+TX,Micromonospora coerulea+TX, Microsphaeropsis ochracea+TX, Muscodor albus620 (Muscudor®)+TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp.(AMykor®+TX, Root Maximizer®)+TX, Myrothecium verrucaria strainAARC-0255 (DiTera®)+TX, BROS PLUS®+TX, Ophiostoma piliferum strain D97(Sylvanex®)+TX, Paecilomyces farinosus+TX, Paecilomyces fumosoroseus(PFR-97®+TX, PreFeRal®)+TX, Paecilomyces linacinus (Biostat WP®)+TX,Paecilomyces lilacinus strain 251 (MeloCon WG®)+TX, Paenibacilluspolymyxa+TX, Pantoea agglomerans (BlightBan C9-1®)+TX, Pantoea spp.+TX,Pasteuria spp. (Econem®)+TX, Pasteuria nishizawae+TX, Penicilliumaurantiogriseum+TX, Penicillium billai (Jumpstart®+TX, TagTeam®)+TX,Penicillium brevicompactum+TX, Penicillium frequentans+TX, Penicilliumgriseofulvum+TX, Penicillium purpurogenum+TX, Penicillium spp.+TX,Penicillium viridicatum+TX, Phlebiopsis gigantean (Rotstop®)+TX,phosphate solubilizing bacteria (Phosphomeal®)+TX, Phytophthoracryptogea+TX, Phytophthora palmivora (Devine®)+TX, Pichia anomala+TX,Pichia guilermondii+TX, Pichia membranaefaciens+TX, Pichia onychis+TX,Pichia stipites+TX, Pseudomonas aeruginosa+TX, Pseudomonas aureofasciens(Spot-Less Biofungicide®)+TX, Pseudomonas cepacia+TX, Pseudomonaschlororaphis (AtEze®)+TX, Pseudomonas corrugate+TX, Pseudomonasfluorescens strain A506 (BlightBan A506®)+TX, Pseudomonas putida+TX,Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae(Bio-Save®)+TX, Pseudomonas viridiflava+TX, Pseudomons fluorescens(Zequanox®)+TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®)+TX,Puccinia canaliculata+TX, Puccinia thlaspeos (Wood Warrior®)+TX, Pythiumparoecandrum+TX, Pythium oligandrum (Polygandron®+TX, Polyversum®)+TX,Pythium periplocum+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia(Dormal®+TX, Vault®)+TX, Rhizoctonia+TX, Rhodococcus globerulus strainAQ719+TX, Rhodosporidium diobovatum+TX, Rhodosporidium toruloides+TX,Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX,Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomycescerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotiniaminor (SARRITOR®)+TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX,Spodoptera exigua nuclear polyhedrosis virus (Spod-X®+TX, Spexit®)+TX,Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX,Sordaria fimicola+TX, Spodoptera littoralis nucleopolyhedrovirus(Littovir®)+TX, Sporobolomyces roseus+TX, Stenotrophomonasmaltophilia+TX, Streptomyces ahygroscopicus+TX, Streptomycesalbaduncus+TX, Streptomyces exfoliates+TX, Streptomyces galbus+TX,Streptomyces griseoplanus+TX, Streptomyces griseoviridis (Mycostop®)+TX,Streptomyces lydicus (Actinovate®)+TX, Streptomyces lydicus WYEC-108(ActinoGrow®)+TX, Streptomyces violaceus+TX, Tilletiopsis minor+TX,Tilletiopsis spp.+TX, Trichoderma asperellum (T34 Biocontrol®)+TX,Trichoderma gamsii (Tenet®)+TX, Trichoderma atroviride (Plantmate®)+TX,Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai(Mycostar®)+TX, Trichoderma harzianum T-22 (Trianum-P®+TX, PlantShieldHCO+TX, RootShield®+TX, Trianum-G®)+TX, Trichoderma harzianum T-39(Trichodex®)+TX, Trichoderma inhamatum+TX, Trichoderma koningii+TX,Trichoderma spp. LC 52 (Sentinel®)+TX, Trichoderma lignorum+TX,Trichoderma longibrachiatum+TX, Trichoderma polysporum (Binab T®)+TX,Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerlyGliocladium virens GL-21) (SoilGuard®)+TX, Trichoderma viride+TX,Trichoderma viride strain ICC 080 (Remedier®)+TX, Trichosporonpullulans+TX, Trichosporon spp.+TX, Trichothecium spp.+TX, Trichotheciumroseum+TX, Typhula phacorrhiza strain 94670+TX, Typhula phacorrhizastrain 94671+TX, Ulocladium atrum+TX, Ulocladium oudemansii(Botry-Zen®)+TX, Ustilago maydis+TX, various bacteria and supplementarymicronutrients (Natural II®)+TX, various fungi (MillenniumMicrobes®)+TX, Verticillium chlamydosporium+TX, Verticillium lecanii(Mycotal®+TX, Vertalec®)+TX, Vip3Aa20 (VIPtera®)+TX, Virgibaclillusmarismortui+TX, Xanthomonas campestris pv. Poae (Camperico®)+TX,Xenorhabdus bovienii+TX, Xenorhabdus nematophilus;Plant extracts including: pine oil (Retenol®)+TX, azadirachtin (PlasmaNeem Oil®+TX, AzaGuard®+TX, MeemAzal®+TX, Molt-X®+TX, Botanical IGR(Neemazad®+TX, Neemix®)+TX, canola oil (Lilly Miller Vegol®)+TX,Chenopodium ambrosioides near ambrosioides (Requiem®)+TX, Chrysanthemumextract (Crisant®)+TX, extract of neem oil (Trilogy®)+TX, essentialsoils of Labiatae (Botania®)+TX, extracts of clove rosemary peppermintand thyme oil (Garden Insect Killer®)+TX, Glycinebetaine(Greenstim®)+TX, garlic+TX, lemongrass oil (GreenMatch®)+TX, neemoil+TX, Nepeta cataria (Catnip oil)+TX, Nepeta catarina+TX, nicotine+TX,oregano oil (MossBuster®)+TX, Pedaliaceae oil (Nematon®)+TX,pyrethrum+TX, Quillaja saponaria (NemaQ®)+TX, Reynoutria sachalinensis(Regalia®+TX, Sakalia®)+TX, rotenone (Eco Roten®)+TX, Rutaceae plantextract (Soleo®)+TX, soybean oil (Ortho Ecosense®)+TX, tea tree oil(Timorex Gold®)+TX, thymus oil+TX, AGNIQUE® MMF+TX, BugOil®+TX, mixtureof rosemary sesame peppermint thyme and cinnamon extracts (EF 300®)+TX,mixture of clove rosemary and peppermint extract (EF 400®)+TX, mixtureof clove peppermint garlic oil and mint (Soil Shot®)+TX, kaolin(Screen®)+TX, storage glucam of brown algae (Laminarin®);pheromones including: blackheaded fireworm pheromone (3M SprayableBlackheaded Fireworm Pheromone®)+TX, Codling Moth Pheromone (Paramountdispenser-(CM)/Isomate C-Plus®)+TX, Grape Berry Moth Pheromone (3MMEC-GBM Sprayable Pheromone®)+TX, Leafroller pheromone (3M MEC—LRSprayable Pheromone®)+TX, Muscamone (Snip7 Fly Bait®+TX, Starbar PremiumFly Bait®)+TX, Oriental Fruit Moth Pheromone (3M Oriental Fruit MothSprayable Pheromone®)+TX, Peachtree Borer Pheromone (Isomate-P®)+TX,Tomato Pinworm Pheromone (3M Sprayable Pheromone®)+TX, Entostat powder(extract from palm tree) (Exosex CM®)+TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11Tetradecatrienyl acetate+TX,(Z+TX,Z+TX,E)-7+TX,11+TX,13-Hexadecatrienal+TX,(E+TX,Z)-7+TX,9-Dodecadien-1-yl acetate+TX, 2-Methyl-1-butanol+TX,Calcium acetate+TX, Scenturion®+TX, Biolure®+TX, Check-Mate®+TX,Lavandulyl senecioate, Macrobials including: Aphelinus abdominalis+TX,Aphidius ervi (Aphelinus-System®)+TX, Acerophagus papaya+TX, Adaliabipunctata (Adalia-System®)+TX, Adalia bipunctata (Adaline®)+TX, Adaliabipunctata (Aphidalia®)+TX, Ageniaspis citricola+TX, Ageniaspisfuscicollis+TX, Amblyseius andersoni (Anderline®+TX,Andersoni-System®)+TX, Amblyseius californicus (Amblyline®+TX,Spical®)+TX, Amblyseius cucumeris (Thripex®+TX, Bugline Cucumeris®)+TX,Amblyseius fallacis (Fallacis®)+TX, Amblyseius swirskii (BuglineSwirskii®+TX, Swirskii-Mite®)+TX, Amblyseius womersleyi (WomerMite®)+TX,Amitus hesperidum+TX, Anagrus atomus+TX, Anagyrus fusciventris+TX,Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococci(Citripar®)+TX, Anicetus benefices+TX, Anisopteromalus calandrae+TX,Anthocoris nemoralis (Anthocoris-System®)+TX, Aphelinus abdominalis(Apheline®+TX, Aphiline®)+TX, Aphelinus asychis+TX, Aphidius colemani(Aphipar®)+TX, Aphidius ervi (Ervipar®)+TX, Aphidius gifuensis+TX,Aphidius matricariae (Aphipar-M®)+TX, Aphidoletes aphidimyza(Aphidend®)+TX, Aphidoletes aphidimyza (Aphidoline®)+TX, Aphytislingnanensis+TX, Aphytis melinus+TX, Aprostocetus hagenowii+TX, Athetacoriaria (Staphyline®)+TX, Bombus spp.+TX, Bombus terrestris (NatupolBeehive®)+TX, Bombus terrestris (Beeline®+TX, Tripol®)+TX, Cephalonomiastephanoderis+TX, Chilocorus nigritus+TX, Chrysoperla carnea(Chrysoline®)+TX, Chrysoperla carnea (Chrysopa®)+TX, Chrysoperlarufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilus quadristriatus+TX,Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX,Closterocerus spp.+TX, Coccidoxenoides perminutus (Planopar®)+TX,Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Cotesia flavipes+TX,Cotesia plutellae+TX, Cryptolaemus montrouzieri (Cryptobug®+TX,Cryptoline®)+TX, Cybocephalus nipponicus+TX, Dacnusa sibirica+TX,Dacnusa sibirica (Minusa®)+TX, Diglyphus isaea (Diminex®)+TX, Delphastuscatalinae (Delphastus®)+TX, Delphastus pusillus+TX, Diachasmimorphakrausii+TX, Diachasmimorpha longicaudata+TX, Diaparsis jucunda+TX,Diaphorencyrtus aligarhensis+TX, Diglyphus isaea+TX, Diglyphus isaea(Miglyphus®+TX, Digline®)+TX, Dacnusa sibirica (DacDigline®+TX,Minex®)+TX, Diversinervus spp.+TX, Encarsia citrina+TX, Encarsia formosa(Encarsia Max®+TX, Encarline®+TX, En-Strip®)+TX, Eretmocerus eremicus(Enermix®)+TX, Encarsia guadeloupae+TX, Encarsia haitiensis+TX,Episyrphus balteatus (Syrphidend®)+TX, Eretmoceris siphonini+TX,Eretmocerus californicus+TX, Eretmocerus eremicus (Ercal®+TX, Eretlinee®)+TX, Eretmocerus eremicus (Bemimix®)+TX, Eretmocerus hayati+TX,Eretmocerus mundus (Bemipar®+TX, Eretline m®)+TX, Eretmocerussiphonini+TX, Exochomus quadripustulatus+TX, Feltiella acarisuga(Spidend®)+TX, Feltiella acarisuga (Feltiline®)+TX, Fopius arisanus+TX,Fopius ceratitivorus+TX, Formononetin (Wirless Beehome®)+TX,Franklinothrips vespiformis (Vespop®)+TX, Galendromus occidentalis+TX,Goniozus legneri+TX, Habrobracon hebetor+TX, Harmonia axyridis(HarmoBeetle®)+TX, Heterorhabditis spp. (Lawn Patrol®)+TX,Heterorhabditis bacteriophora (NemaShield HB®+TX, Nemaseek®+TX,Terranem-Nam®+TX, Terranem®+TX, Larvanem®+TX, B-Green®+TX,NemAttack®+TX, Nematop®)+TX, Heterorhabditis megidis (Nemasys H®+TX,BioNem H®+TX, Exhibitline hm®+TX, Larvanem-M®)+TX, Hippodamiaconvergens+TX, Hypoaspis aculeifer (Aculeifer-System®+TX,Entomite-A®)+TX, Hypoaspis miles (Hypoline m®+TX, Entomite-M®)+TX,Lbalia leucospoides+TX, Lecanoideus floccissimus+TX, Lemophaguserrabundus+TX, Leptomastidea abnormis+TX, Leptomastix dactylopii(Leptopar®)+TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexisoregmae+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebus testaceipes+TX,Macrolophus caliginosus (Mirical-N®+TX, Macroline c®+TX, Mirical®)+TX,Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX,Micromus angulatus (Milacewing®)+TX, Microterys flavus+TX, Muscidifuraxraptorellus and Spalangia cameroni (Biopar®)+TX, Neodryinustyphlocybae+TX, Neoseiulus californicus+TX, Neoseiulus cucumeris(THRYPEX®)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis(NesidioBug®+TX, Nesibug®)+TX, Ophyra aenescens (Biofly®)+TX, Oriusinsidiosus (Thripor-I®+TX, Oriline i®)+TX, Orius laevigatus(Thripor-L®+TX, Oriline I®)+TX, Orius majusculus (Oriline m®)+TX, Oriusstrigicollis (Thripor-S®)+TX, Pauesia juniperorum+TX, Pediobiusfoveolatus+TX, Phasmarhabditis hermaphrodita (Nemaslug®)+TX,Phymastichus coffea+TX, Phytoseiulus macropilus+TX, Phytoseiuluspersimilis (Spidex®+TX, Phytoline p®)+TX, Podisus maculiventris(Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX,Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastixmexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX,Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia cardinalis+TX,Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae(Ervibank®)+TX, Steinernema carpocapsae (Nematac C®+TX, Millenium®+TX,BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®)+TX, Steinernemafeltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX,Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline sf®+TX,Scia-Rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNemL®+TX, Exhibitline srb®)+TX, Steinernema riobrave (BioVector®+TX,BioVektor®)+TX, Steinernema scapterisci (Nematac S®)+TX, Steinernemaspp.+TX, Steinernematid spp. (Guardian Nematodes®)+TX, Stethoruspunctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastichussetifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogrammabrassicae (Tricholine b®)+TX, Trichogramma brassicae (Tricho-Strip®)+TX,Trichogramma evanescens+TX, Trichogramma minutum+TX, Trichogrammaostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX,Xanthopimpla stemmator; andother biologicals including: abscisic acid+TX, bioSea®+TX,Chondrostereum purpureum (Chontrol Paste®)+TX, Colletotrichumgloeosporioides (Collego®)+TX, Copper Octanoate (Cueva®)+TX, Delta traps(Trapline d®)+TX, Erwinia amylovora (Harpin) (ProAct®+TX, Ni-HIBIT GoldCST®)+TX, Ferri-phosphate (Ferramol®)+TX, Funnel traps (Trapline y®)+TX,Gallex®+TX, Grower's Secret®+TX, Homo-brassonolide+TX, Iron Phosphate(Lilly Miller Worry Free Ferramol Slug & Snail Bait®)+TX, MCP hail trap(Trapline f®)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris(Des-X®)+TX, BioGain®+TX, Aminomite®+TX, Zenox®+TX, Pheromone trap(Thripline ams®)+TX, potassium bicarbonate (MilStop®)+TX, potassiumsalts of fatty acids (Sanova®)+TX, potassium silicate solution(Sil-Matrix®)+TX, potassium iodide+potassiumthiocyanate (Enzicur®)+TX,SuffOil-X®+TX, Spider venom+TX, Nosema locustae (Semaspore OrganicGrasshopper Control®)+TX, Sticky traps (Trapline YF®+TX, RebellAmarillo®)+TX and Traps (Takitrapline y+b®)+TX.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. The abovedescribed mixing partners are known. Where the active ingredients areincluded in “The Pesticide Manual” [The Pesticide Manual—A WorldCompendium; Thirteenth Edition; Editor: C. D. S. TomLin; The BritishCrop Protection Council], they are described therein under the entrynumber given in round brackets hereinabove for the particular compound;for example, the compound “abamectin” is described under entry number(1). Where “[CCN]” is added hereinabove to the particular compound, thecompound in question is included in the “Compendium of Pesticide CommonNames”, which is accessible on the internet [A. Wood; Compendium ofPesticide Common Names, Copyright © 1995-2004]; for example, thecompound “acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “development code”is used or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed. “CAS Reg. No” means theChemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula I selectedfrom the compounds defined in the Tables A-1 to A-120 and Table P andwith active ingredients described above comprises a compound selectedfrom one compound defined in the Tables A-1 to A-120 and Table P and anactive ingredient as described above preferably in a mixing ratio offrom 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in aratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, veryespecially from 5:1 and 1:5, special preference being given to a ratioof from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 being likewisepreferred, above all in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4,or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5,or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75,or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750,or 2:750, or 4:750. Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controllingpests, which comprises applying a composition comprising a mixture asdescribed above to the pests or their environment, with the exception ofa method for treatment of the human or animal body by surgery or therapyand diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of formula I selected from thecompounds defined in the Tables A-1 to A-120 and Table P and one or moreactive ingredients as described above can be applied, for example, in asingle “ready-mix” form, in a combined spray mixture composed fromseparate formulations of the single active ingredient components, suchas a “tank-mix”, and in a combined use of the single active ingredientswhen applied in a sequential manner, i.e. one after the other with areasonably short period, such as a few hours or days. The order ofapplying the compounds of formula I and the active ingredients asdescribed above is not essential for working the present invention.

The compositions according to the invention can also comprise furthersolid or liquid auxiliaries, such as stabilizers, for exampleunepoxidized or epoxidized vegetable oils (for example epoxidizedcoconut oil, rapeseed oil or soya oil), antifoams, for example siliconeoil, preservatives, viscosity regulators, binders and/or tackifiers,fertilizers or other active ingredients for achieving specific effects,for example bactericides, fungicides, nematocides, plant activators,molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compounds of formula I of the invention and compositions thereof arealso be suitable for the protection of plant propagation material, forexample seeds, such as fruit, tubers or kernels, or nursery plants,against pests of the abovementioned type. The propagation material canbe treated with the compound prior to planting, for example seed can betreated prior to sowing. Alternatively, the compound can be applied toseed kernels (coating), either by soaking the kernels in a liquidcomposition or by applying a layer of a solid composition. It is alsopossible to apply the compositions when the propagation material isplanted to the site of application, for example into the seed furrowduring drilling. These treatment methods for plant propagation materialand the plant propagation material thus treated are further subjects ofthe invention. Typical treatment rates would depend on the plant andpest/fungi to be controlled and are generally between 1 to 200 grams per100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds,such as between 10 to 100 grams per 100 kg of seeds.

The term seed embraces seeds and plant propagules of all kinds includingbut not limited to true seeds, seed pieces, suckers, corns, bulbs,fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like andmeans in a preferred embodiment true seeds.

The present invention also comprises seeds coated or treated with orcontaining a compound of formula I. The term “coated or treated withand/or containing” generally signifies that the active ingredient is forthe most part on the surface of the seed at the time of application,although a greater or lesser part of the ingredient may penetrate intothe seed material, depending on the method of application. When the saidseed product is (re)planted, it may absorb the active ingredient. In anembodiment, the present invention makes available a plant propagationmaterial adhered thereto with a compound of formula I. Further, it ishereby made available, a composition comprising a plant propagationmaterial treated with a compound of formula I.

Seed treatment comprises all suitable seed treatment techniques known inthe art, such as seed dressing, seed coating, seed dusting, seed soakingand seed pelleting. The seed treatment application of the compoundformula I can be carried out by any known methods, such as spraying orby dusting the seeds before sowing or during the sowing/planting of theseeds.

The disclosure in the present application makes available each and everycombination of embodiments disclosed herein.

It should be noted that the disclosure herein in respect of a compoundof formula I applies equally in respect of a compound of each offormulae I*, I′a, and Tables A-1 to A-120.

The compounds of the invention can be distinguished from other similarcompounds by virtue of greater efficacy at low application rates and/ordifferent pest control, which can be verified by the person skilled inthe art using the experimental procedures, using lower concentrations ifnecessary, for example 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lowerapplication rates, such as 300, 200 or 100, mg of Al per m². The greaterefficacy can be observed by an increased safety profile (againstnon-target organisms above and below ground (such as fish, birds andbees), improved physico-chemical properties, or increasedbiodegradability).

BIOLOGICAL EXAMPLES

The Examples which follow serve to illustrate the invention. Certaincompounds of the invention can be distinguished from known compounds byvirtue of greater efficacy at low application rates, which can beverified by the person skilled in the art using the experimentalprocedures outlined in the

Example B1: Bemisia tabaci (Cotton White Fly): Feeding/Contact Activity

Cotton leaf discs were placed on agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10,000 ppm DMSO stocksolutions. After drying the leaf discs were infested with adult whiteflies. The samples were checked for mortality 6 days after incubation.

Example B2: Diabrotica Balteata (Corn Root Worm)

Maize sprouts placed onto an agar layer in 24-well microtiter plateswere treated with aqueous test solutions prepared from 10,000 ppm DMSOstock solutions by spraying. After drying, the plates were infested withL2 larvae (6 to 10 per well). The samples were assessed for mortalityand growth inhibition in comparison to untreated samples 4 days afterinfestation.

The following compounds gave an effect of at least 80% control in atleast one of the two categories (mortality or growth inhibition) at anapplication rate of 200 ppm:

P3, P4, P5, P6, P7, P8, P9, P11. Example B3: Euschistusheros(Neotropical Brown Stink Bug)

Soybean leaves on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10,000 ppm DMSO stock solutions.After drying the leaves were infested with N2 nymphs. The samples wereassessed for mortality and growth inhibition in comparison to untreatedsamples 5 days after infestation.

The following compounds gave an effect of at least 80% control in atleast one of the two categories (mortality or growth inhibition) at anapplication rate of 200 ppm:

P3, P5, P6. Example B4: Frankliniella occidentalis (Western FlowerThrips): Feeding/Contact Activity

Sunflower leaf discs were placed on agar in 24-well microtiter platesand sprayed with aqueous test solutions prepared from 10,000 DMSO stocksolutions. After drying the leaf discs were infested with aFrankliniella population of mixed ages. The samples were assessed formortality 7 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm:

Example B5: Plutella xylostella (Diamond Back Moth)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10,000 ppm DMSO stock solutions bypipetting. After drying, Plutella eggs were pipetted through a plasticstencil onto a gel blotting paper and the plate was closed with it. Thesamples were assessed for mortality and growth inhibition in comparisonto untreated samples 8 days after infestation.

The following compounds gave an effect of at least 80% control in atleast one of the two categories (mortality or growth inhibition) at anapplication rate of 200 ppm:

P3, P4, P5, P6, P7, P8, P9, P10, P11, P12. Example B6: Myzus persicae(Green Peach Aphid):Feeding/Contact Activity

Sunflower leaf discs were placed onto agar in a 24-well microtiter plateand sprayed with aqueous test solutions prepared from 10,000 ppm DMSOstock solutions. After drying, the leaf discs were infested with anaphid population of mixed ages. The samples were assessed for mortality6 days after infestation.

Example B7: Myzus persicae (Green Peach Aphid). Systemic Activity

Roots of pea seedlings infested with an aphid population of mixed ageswere placed directly into aqueous test solutions prepared from 10,000DMSO stock solutions. The samples were assessed for mortality 6 daysafter placing seedlings into test solutions.

Example B8: Myzus persicae (Green Peach Aphid). Intrinsic Activity

Test compounds prepared from 10,000 ppm DMSO stock solutions wereapplied by pipette into 24-well microtiter plates and mixed with sucrosesolution. The plates were closed with a stretched Parafilm. A plasticstencil with 24 holes was placed onto the plate and infested peaseedlings were placed directly on the Parafilm. The infested plate wasclosed with a gel blotting paper and another plastic stencil and thenturned upside down. The samples were assessed for mortality 5 days afterinfestation.

The following compounds resulted in at least 80% mortality at a testrate of 12 ppm:

P3, P12. Example B9: Plutella xylostella (Diamond Back Moth)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10,000 ppm DMSO stock solutions bypipetting. After drying, the plates were infested with L2 larvae (10 to15 per well). The samples were assessed for mortality and growthinhibition in comparison to untreated samples 5 days after infestation.

Example B10: Spodoptera littoralis (Egyptian Cotton Leaf Worm)

Cotton leaf discs were placed onto agar in 24-well microtiter plates andsprayed with aqueous test solutions prepared from 10,000 ppm DMSO stocksolutions. After drying the leaf discs were infested with five L1larvae. The samples were assessed for mortality, anti-feeding effect,and growth inhibition in comparison to untreated samples 3 days afterinfestation. Control of Spodoptera littoralis by a test sample is givenwhen at least one of the categories mortality, anti-feedant effect, andgrowth inhibition is higher than the untreated sample.

The following compounds resulted in at least 80% control in at least oneof the three categories (mortality, anti-feeding, or growth inhibition)at an application rate of 200 ppm:

P3, P4, P5, P6, P7, P8, P9, P11, P12. Example B11: Tetranychus urticae(Two-Spotted Spider Mite):Feeding/Contact Activity

Bean leaf discs on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10,000 ppm DMSO stock solutions.After drying the leaf discs were infested with a mite population ofmixed ages. The samples were assessed for mortality on mixed population(mobile stages) 8 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 200 ppm:

P6. Example B12: Thrips tabaci (Onion Thrips) Feeding/Contact Activity

Sunflower leaf discs were placed on agar in 24-well microtiter platesand sprayed with aqueous test solutions prepared from 10,000 ppm DMSOstock solutions. After drying the leaf discs were infested with a thripspopulation of mixed ages. The samples were assessed for mortality 6 daysafter infestation.

Example B13: Plutella xylostella (Diamondback Moth)

96-well microtiter plates containing artificial diet were treated withaqueous test solutions, prepared from 10,000 ppm DMSO stock solutions,by a liquid handling robot. After drying, eggs (˜30 per well) wereinfested onto a netted lid which was suspended above the diet. The eggshatch and L1 larvae move down to the diet. The samples were assessed formortality 9 days after infestation.

The following compounds gave an effect of at least 80% mortality at anapplication rate of 500 ppm:

P6, P10, P11. Example 14: Chilo suppressalis (Striped Rice Stemborer)

24-well microtiter plates with artificial diet were treated with aqueoustest solutions prepared from 10,000 ppm DMSO stock solutions bypipetting. After drying, the plates were infested with L2 larvae (6-8per well). The samples were assessed for mortality, anti-feeding effect,and growth inhibition in comparison to untreated samples 6 days afterinfestation. Control of Chilo suppressalis by a test sample is givenwhen at least one of the categories mortality, anti-feedant effect, andgrowth inhibition is higher than the untreated sample.

The following compounds resulted in at least 80% control in at least oneof the three categories (mortality, anti-feeding or growth inhibition)at an application rate of 200 ppm:

P3, P4, P5, P6, P8, P9, P10, P11, P12.

1. A compound of the formula I

wherein: A₁ is N or CH; R₁ is hydrogen, C₁-C₆alkyl, C₁-C₆cyanoalkyl, aminocarbonylC₁-C₆alkyl, hydroxycarbonylC₁-C₆alkyl, C₁-C₆nitroalkyl, trimethylsilaneC₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl; C₃-C₄cycloalkylC₁-C₂alkyl- wherein the C₃-C₄cycloalkyl is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH₂—; or benzyl optionally substituted with halo or C₁-C₆haloalkyl; R₂ is phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents, provided the substituent(s) are not on either carbon adjacent to the carbon C═O is attached, and each substituent is independently selected from: C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃thiohaloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, NO₂, SF₅, CN, CONH₂, COOH and C(S)NH₂; R₃ is C₁-C₃alkyl or C₁-C₃haloalkyl; R₄ is C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₄halocycloalkyl, or C₃-C₆cycloalkylC₁-C₄haloalkyl; R₅ is H, C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl, C₁-C₃alkoxy, C₁-C₃alkoxycarbonyl, or di(C₁-C₃alkoxy)methine; or a stereoisomer, enantiomer, tautomer and N-oxide of the compound of formula I, or agrochemically acceptable salt thereof.
 2. A compound according to claim 1 wherein A₁ is N or CH; R₁ is hydrogen, C₁-C₆alkyl, C₁-C₆cyanoalkyl, aminocarbonylC₁-C₆alkyl, hydroxycarbonylC₁-C₆alkyl, C₁-C₆nitroalkyl, trimethylsilaneC₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl; C₃-C₄cycloalkylC₁-C₂alkyl- wherein the C₃-C₄cycloalkyl is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH₂—; or benzyl optionally substituted with halo or C₁-C₆haloalkyl; R₂ is K₁, K₂, K₄ to K₂₁; R₃ is C₁-C₃alkyl or C₁-C₃haloalkyl; R₄ is C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₄halocycloalkyl, or C₃-C₆cycloalkylC₁-C₄haloalkyl; R₅ is H, C₁-C₃alkyl, C₁-C₃haloalkyl, C₃-C₄cycloalkyl, C₁-C₃alkoxy, C₁-C₃alkoxycarbonyl, or di(C₁-C₃alkoxy)methine; or a stereoisomer, enantiomer, tautomer and N-oxide of the compound of formula I, or agrochemically acceptable salt thereof;


3. The compound according to claim 1, wherein R₁ is hydrogen, cyclopropyl-CH₂—, hydrogen or CH₃
 4. The compound according to claim 1, wherein R₃ is C₁-C₃alkyl.
 5. The compound according to claim 1, wherein R₄ is selected from C₂-C₄fluoroalkenyl, or C₂-C₄fluoroalkynyl
 6. The compound according to claim 1, wherein R₄ is selected from 3,3,3-trifluoroprop-1-enoxy.
 7. The compound according to claim 2, wherein R₄ is selected C₁-C₄fluoroalkyl.
 8. The compound according to claim 2, wherein R₂ is K₁, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or K₂₁.
 9. A composition comprising a compound according to claim 1, one or more auxiliaries and diluent, and optionally one more other active ingredient.
 10. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound according to claim
 1. 11. A method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with an effective amount of a compound according to claim
 1. 12. A plant propagation material comprising, or treated with or adhered thereto, a compound according to claim
 1. 13. A method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound according to claim
 1. 14. A compound of formula IIa

wherein R₁ is hydrogen, C₁-C₆alkyl, C₁-C₆cyanoalkyl, aminocarbonylC₁-C₆alkyl, hydroxycarbonylC₁-C₆alkyl, C₁-C₆nitroalkyl, trimethylsilaneC₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl; C₃-C₄cycloalkylC₁-C₂alkyl- wherein the C₃-C₄cycloalkyl is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH₂—; or benzyl optionally substituted with halo or C₁-C₆haloalkyl and R_(4a) is selected from J₅, J₇ to J₁₀


15. A compound of formula XXa

wherein R₁ is hydrogen, C₁-C₆alkyl, C₁-C₆cyanoalkyl, aminocarbonylC₁-C₆alkyl, hydroxycarbonylC₁-C₆alkyl, C₁-C₆nitroalkyl, trimethylsilaneC₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl; C₃-C₄cycloalkylC₁-C₂alkyl- wherein the C₃-C₄cycloalkyl is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH₂—; or benzyl optionally substituted with halo or C₁-C₆haloalkyl, A₁ is either N or CH; and R₂ is phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents, provided the substituent(s) are not on either carbon adjacent to the carbon C═O is attached, and each substituent is independently selected from: C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃thiohaloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, NO₂, SF₅, CN, CONH₂, COOH and C(S)NH₂.
 16. The compound according to claim 7, wherein R₂ is K₁, K₅, K₆, K₁₁, K₁₂, K₁₃, K₁₅, K₁₆, K₁₈, K₁₉, K₂₀, or K₂₁.
 17. The compound according to claim 14, wherein R₁ is hydrogen, cyclopropyl-CH₂—, hydrogen or CH₃.
 18. The compound according to claim 15, wherein R₁ is hydrogen, cyclopropyl-CH₂—, hydrogen or CH₃.
 19. The compound according to claim 15, wherein R₂ is K₁, K₂, K₄ to K₂₁:


20. The compound according to claim 19, wherein R₁ is hydrogen, cyclopropyl-CH₂—, hydrogen or CH₃.
 21. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a composition according to claim
 9. 22. A method for the protection of plant propagation material from the attack by insects, acarines, nematodes or molluscs, which comprises treating the propagation material or the site, where the propagation material is planted, with an effective amount of a composition according to claim
 9. 23. A plant propagation material comprising, or treated with or adhered thereto, a composition according to claim
 9. 24. A method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a composition according to claim
 9. 